Porphyrin dimers and arrays

FULL PAPER

DOI: 10.1002/ejoc.201100642

Porphyrin Dimers and Arrays^[‡]

Aoife Ryan,^[a]Andreas Gehrold,^[a]Romain Perusitti,^[a]Monica Pintea,^[a]

Marijana Fazekas,^[a]Oliver B. Locos,^[a]Frances Blaikie,^[a]and Mathias O. Senge*^[a,b]

Dedicated to Professor Gerhard Bringmann on the occasion of his 60th birthday

Keywords: Porphyrinoids / Nitrogen heterocycles / C–C coupling / Nonlinear optics / Photodynamic therapy

Current applications of porphyrins in medicine and optics,

such as photodynamic therapy or nonlinear absorbers, in-

creasingly require the use of far-red absorbing dyes. Modifi-

cations of the porphyrin structure to accommodate these con-

ditions can be achieved by extending the conjugation of the

porphyrin π-system, which causes a bathochromic shift in the

absorption spectrum. Thus, conjugated porphyrin oligomers

have found widespread use. However, past synthetic strate-

gies have mainly targeted symmetric porphyrin dimers, tri-

mers, and oligomers, which limit the practical use of such

chromophores. Here, a series of symmetric and unsymmetric

dimeric and trimeric porphyrin systems, which are connected

by conjugated linkers, namely alkyne and phenylacetylene,

were synthesized by palladium-catalyzed C–C coupling re-

actions. Adopting two approaches, firstly, a series of new un-

symmetric dimers was synthesized by the incorporation of all

substituents on the monomeric components prior to coupling.

The second was the synthesis of new symmetric dimers and

trimers with free meso positions enabling further chemistry

to be carried out. The majority of these conjugated arrays

exhibited a bathochromic shift in their UV/Vis absorption, in

particular the alkyne-linked arrays showed absorption

greater than 720 nm. The mass spectra of phenylacetylene-

and diphenylbutadiene-linked zinc arrays exhibited detach-

ment of zinc from the porphyrin core. These unusual results

are both linker and metal dependent, usually only seen for

more labile metals.

Introduction

photosensitizers show absorption in 530 to 630 nm range,

which limits the penetration of tissue by light.^[8,9]Increasing

the absorption wavelength of the photosensitizer may en-

able deeper penetration and therefore the targeting of

deeper tumors. Here conjugated dimers and trimers are

ideal potential photosensitizer candidates as their absorp-

tion maximum should exhibit a bathochromic shift to this

region. The type of linkage in the porphyrin arrays will in-

fluence the structure and properties of the system, so by

extending the conjugation of the porphyrin π-system, and

hence increasing the wavelength absorption, these oligo-

mers could be used as potential photosensitizers for PDT

or for other optical applications. Recent work by Anderson

et al. displays this concept, whereby butadiyne-linked di-

mers were synthesized and tested for in vitro PDT.^[10]Our

aim is to synthesize new alkyne and phenylacetylene-linked

arrays and further develop the synthetic chemistry for un-

symmetrical array systems. As the delocalization of elec-

trons extends into this alkyne spacer group, these arrays are

Multiporphyrin arrays have a wide range of potential ap-

plications in areas such as light harvesting, nonlinear optics

(NLO), organic light-emitting diodes (OLEDs), and photo-

dynamic therapy (PDT). Hence, these systems have been

investigated widely.^[1–5]Despite the vast knowledge and in-

vestigations of such arrays, the majority of work involves

studies of symmetric multiporphyrin systems. Although

these are also of interest to our area of research, our main

focus was on unsymmetrical arrays, through which amphi-

philicity for PDT could be enhanced or, with respect to

NLO, push–pull systems could be arranged through this

unsymmetry. An example for the latter strategy has been

given in another paper.^[6]

We are interested in NLO materials^[2a,2e]and have initi-

ated a program aiming at the development of new photo-

sensitizers for PDT.^[5d,7]Current commercially available

[‡] Synthesis of Unsymmetrical meso-Substituted Porphyrins, 2.

Part 1: Ref.^[6]

[a] School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity linear and sterically undemanding.^[11]Hence, the communi-

College Dublin,

cation between the chromophores should be efficient mak-

ing them attractive for not only for PDT but also for NLO,

OLED, and other light harvesting applications.

Our approach incorporated two ideas: the first was the

synthesis of unsymmetric dimers, namely alkyne-linked ar-

Dublin 2, Ireland

Fax: +353-1-896-8536

E-mail: sengem@tcd.ie

[b] Medicinal Chemistry, Institute of Molecular Medicine, Trinity

Centre for Health Sciences, Trinity College Dublin,

St James’s Hospital, Dublin 8, Ireland

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rays. These unsymmetric dimers can contain both hydrophil- cedure^[18]forming 9–13^[19a,18,20]in yields of 60–95%, the

ic and hydrophobic entities at the various meso positions lower yields being those of monobrominated porphyrins

(Figure 1), whereby the amphiphilicity is enhanced, thus, in 9^[19]and 12. Monobromination of 5,15-disubstituted por-

theory, assisting with the entry of the photosensitizer into phyrins is quite difficult to achieve in good yields due to

the cell target.^[12]The second approach was to synthesize the fact that dibrominated porphyrins are formed as side

symmetric conjugated porphyrin dimers and trimers with products. However, these monobrominated porphyrin

free meso positions. Linear, trimeric arrays with such link- monomers were vital for subsequent coupling reactions to

ers, in particular the phenylacetylene linker, have not been form the linear oligomers, and the dibrominated porphyrins

investigated to a great extent, with only two such com- were used for trimeric array synthesis. Surprisingly, di-

pounds previously synthesized.^[13]Once appropriate lead bromodihexyl 13^[20]proved quite insoluble in many solvents

structures are identified further modifications, e.g. the in- and thus was not used for further reactions. Hence 1-eth-

troduction of water solubilizing groups, are possible at the ylpropyl 11 was used as this proved more soluble in organic

free meso positions to further optimize their biological util- solvents.

ity. Here, we outline the basic chemistry of this approach

using model compounds.

In order to introduce the desired conjugating linker

groups, two approaches were used: 1) arylation (organo-

lithium reaction)^[14]to introduce the phenylacetylene linker

and 2) Sonogashira coupling to introduce the alkyne

linker.^[14,26]Organolithium reactions were carried out on 1–

3 to introduce the phenylacetylene linker and on 1, 2, and

4–8 to introduce various substituents at the meso positions.

Substituents such as methoxyphenyl groups have been

shown to be beneficial for the localization of photosensitiz-

ers in tumors,^[27]so it was envisaged that the introduction

of such substituents would be advantageous. Unless the

organolithium reagent was commercially available it was

generated in situ and then used to attack the porphyrin at

a free meso position to form the desired trisubstituted prod-

uct.^[14a,14b]For phenylacetylene introduction, the reaction

proceeds quite well with phenyl-substituted porphyrins,

forming 29^[14a]in 74% yield. However, this was not the case

for the alkyl-substituted porphyrins, which formed 30 and

31 in yields of 30 and 35%, respectively. The best yield for

30 was obtained when the reaction was left overnight. This

appeared initially to be a solubility problem of 3 in THF,

however, when the solvent volume was increased no im-

provement was seen. Other alterations such as adjusting the

amount of BuLi and altering reaction time had no positive

effect on the reaction yield. Starting materials 2 and 3 were

recovered in approximate yields of 30 and 28%, respectively.

For 1, 2, and 4–8 the trisubstituted porphyrins 32,^[19b]

33, 34 and 35,^[7a]36, 37 and 38,^[7a]40, 42, 44,^[14a]and 45^[6]

were synthesized in yields ranging from 30–84%. Por-

phyrins 5 and 6 yielded the butylated side products 39^[6]

and 41 in yields of 26 and 23%, respectively, along with the

desired trisubstituted 38^[7a]and 40 in yields of 65 and 71%,

respectively. Also, in the synthesis of 36, tetrasubstituted 43

was formed as a side product in 4% yield. These butylated

side products were also used in subsequent reactions for the

synthesis of unsymmetric dimers. Trisubstituted 29 and 32–

41, 44, 45, and 57 were also brominated according to a stan-

dard procedure,^[18]with yields ranging from 55 to 92% for

14–28.^{[21,19b,5d,13a,6]}Both free base and metallated por-

phyrin oligomers were desired and thus 9–11, 15–17, 29,

Figure 1. Model for conjugated unsymmetric dimers.

Results and Discussion

As outlined in the introduction, the synthetic strategy for

the synthesis of conjugated porphyrin oligomers was two-

fold, incorporating both the synthesis of symmetric dimers

and trimers with free meso positions and also the synthesis

of unsymmetric arrays. Both strategies utilized Pd-catalyzed

cross-coupling reactions and the free meso positions on the

symmetric arrays allowed subsequent chemical modifica-

tions to be carried out. In addition, for a comparative mass

spectrometric study, some diphenylbutadiyne and butadiyne

symmetric dimers were synthesized using a Pd-mediated

Glaser coupling method. These arrays can be further modi-

fied due to their free meso positions. Both of these ap-

proaches utilize organolithium methods, developed by

us,^[14]to introduce the phenylacetylene linker and the sub-

stituents on the porphyrin core. Sonogashira coupling was

used to introduce the alkyne linker and for the coupling

reactions.^[15]Some directly linked dimers were also synthe-

sized by Suzuki coupling^[16]to compare their properties to

those oligomers that contain conjugated linkers.

Synthesis of Porphyrin Monomers

5,15-Disubstituted porphyrins^[17]were chosen as the and 30 were metallated with either zinc(II) or nickel(II)^[28]

starting monomers (Scheme 1) to yield linear oligomers giving 46–56^{[18,23,15a,24,25]}in yields of 78–92%.

with free meso positions to enable further chemical modifi-

Porphyrins 9, 10, 15–17, 19, 25, 27, 50, and 52 were sub-

cations, enhancing their possible NLO and PDT effects. jected to Sonogashira coupling^[15]conditions (Scheme 2) to

Porphyrins 1–8 were brominated following a standard pro- form the mono- and disubstituted trimethylsilyl acetylenes

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Unsymmetrical meso-Substituted Porphyrin Dimers and Arrays

Scheme 1. Synthesis of porphyrin precursors. i) R²Li, THF, –70 °C to r.t., NH₄Cl, DDQ. ii) NBS (0.8–2.1 equiv.), CHCl₃, pyridine, 1–

3 h. iii) a) Zn(OAc)₂in MeOH, CHCl₃, 60 °C. b) Ni(acac)₂, toluene, 120 °C, 0.5 h.

59–68^[29–31,6]in yields of 36–83%. An alternative method yields of 82% and 33% from bromoporphyrins 9 and 24

for this synthesis is a one step condensation reaction.^[29]respectively.

This, however, is not applicable for the unsymmetric targets,

In order to construct building blocks for multiporphyrin

thus the stepwise approach was used. With free base por- arrays we choose 5-monosubstituted porphyrins as starting

phyrins 10, 15–17, 19, 25, and 27 there was an inevitable materials.^[35]Of the various possibilities 1-ethylpropyl 81 is

insertion of copper into the core as a side product leading quite soluble.^[35a]As shown in Scheme 4 and Table 1 (see

to slightly lower yields of the desired materials. Metallated Exp. Sect.), this compound allows entry into meso bromo-

porphyrins are usually used under these conditions to avoid substituted porphyrins 82–86 with different regiochemical

this formation, although for 63 this did not increase the arrangements. The selective bromination of porphyrins with

yield significantly. In addition, there is evidence that zinc several unsubstituted meso positions is difficult, but can be

insertion can increase the PDT efficacy.^[32]Porphyrins 59– controlled to some degree depending on the number of

68 were subsequently deprotected using tetrabutylammo- NBS equivalents used.^[13a]This gives an entry into mono-

nium fluoride (TBAF) forming the free alkynyl porphyrins to tribrominated porphyrins. The trans 15-position relative

69–78^[33,29,6]in yields of 61–94%, the lowest yield being that to the alkyl residue appears to be more reactive than the

for hexyl-substituted 73 where much product was lost 10-position.

through recrystallization. Porphyrins 17 and 20 were bo-

The 15-brominated derivative 85 was converted into a

rylated to form the trisubstituted porphyrinyl boronates 79 range of acceptor substituted porphyrins 87–89 in yields of

and 80 by a palladium-catalyzed coupling reaction devel- 24 to 67% using Suzuki coupling conditions. Similar to the

oped by Lin et al.^[15a]and Hasobe et al.^[34]These por- other reactions described above, Sonogashira reactions with

phyrinyl boronates were subsequently used to form directly ethynyltrimethylsilane followed by deprotection with TBAF

linked dimers by Suzuki coupling as shown in Scheme 3.

gave ethynyl-substituted 92 and 93 in good yields

In addition Suzuki coupling was used to introduce the 4- (Scheme 4). The latter is a key intermediate for the prepara-

nitrophenyl substituent, forming prophyrins 57 and 58 in tion of tetrameric porphyrin arrays.

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Scheme 3. Synthesis of directly linked porphyrins by Suzuki cou-

pling. Pd(PPh₃)₄, Cs₂CO₃, toluene, DMF, 80 °C.

Scheme 2. Synthesis of porphyrin precursors by Suzuki or Sono-

gashira coupling and Miyaura borylation. i) TMS-ethyne,

PdCl₂(PPh₃)₂, CuI, Et₃N, THF, 40–60 °C, 16 h. ii) TBAF (1 m in

THF), CH₂Cl₂, 0.5 h, r.t. iii) pinacolborane, Pd(PPh₃)₂, dichloro-

ethane, Et₃N, 80 °C, 16 h. iv) (4-nitrophenyl)boronic acid pinacol

ester, Pd(PPh₃)₄, THF, K₃PO₄, 65 °C, 16 h.

Scheme 4. Synthetic elaboration of a monosubstituted porphyrin.

i) NBS, pyridine, CHCl₃, 0 °C. ii) R¹B(OH)₂, K₃PO₄, Pd(PPh₃)₄,

THF, 12 h. iii) ethynyltrimethylsilane, CuI, Pd(PPh₃)₂Cl₂. iv) 1 m

TBAF solution in THF, CH₂Cl₂.

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Unsymmetrical meso-Substituted Porphyrin Dimers and Arrays

Synthesis of Porphyrin Oligomers

tems, resulting in better absorption in the red region and

hence their possible use as PDT agents.

Depending on the type of oligomer/linker desired, dif-

ferent well established palladium-catalyzed coupling meth-

ods were adopted for the synthesis. The most utilized

method was copper-free Sonogashira coupling and the

others were Suzuki coupling (for the directly linked dimers),

Sonogashira coupling (as a comparative to the copper free

method), and Pd-mediated Glaser coupling for homocou-

pled dimers.^{[15,16,36,37]}

These unsymmetric alkyne-linked dimers were initially

synthesized by original Sonogashira coupling condi-

tions^[15,26]using Pd^IIwith CuCl as a cocatalyst. However,

formation of the homocoupled product 118 as an undesir-

able side product was observed (Scheme 5). This homocou-

pling takes place during the reduction of palladium(II) to

palladium(0), thus it was decided to use a copper-free/Pd⁰

Sonogashira approach.^[36]This coupling protocol yielded

unsymmetric dimers 98–116 in moderate to good yields

ranging from 25–68% (Scheme 6). Generally these dimers

exhibited good solubility in most organic solvents. How-

ever, depending on substituents and in some cases, upon

metallation with zinc, this solubility was somewhat dimin-

ished. This was particularly noticeable for the phenyl-sub-

stituted dimers 110 and 111.

Directly linked dimers: Directly meso–meso linked dimers

were synthesized for comparison to investigate what effect

the linker has on the absorption wavelength. Using Suzuki

coupling methods,^[16,34]directly linked amphiphilic dimers

94–97 were synthesized in yields of 29–51% (Scheme 3).

Porphyrinyl boronates 79 and 80 provided the hydrophobic

entity, and bromoporphyrins 21, 22, and 23 provided the

hydrophilic entity; yields for the 3-methoxyphenyl-substi-

tuted dimers 94 and 97 were lower than those for 4-meth-

oxyphenyl-substituted dimers 95 and 96, most likely due to

the stronger electron-donating effects of the para methoxy

group over the meta group on the porphyrin macrocycle.

Easier purification of hexyl-substituted dimers 96 and 97

was observed due to larger differences in polarity. Although

these arrays do not show much promise as candidates for

PDT due to the lack of a bathochromic shift in their ab-

sorption profile (see UV section), they were of interest for

comparison with the conjugated linked arrays, i.e. to ob-

serve the linker effect on the photophysical properties of the

array.

Alkyne-linked dimers: The first approach mentioned was

to synthesize unsymmetric dimers without any free meso

positions, i.e. the introduction of all substituents prior to

the coupling reaction to form the oligomer. Unsymmetric

alkyne-linked dimers were synthesized to yield larger π-sys-

Scheme 6. Synthesis of unsymmetric alkyne-linked dimers. Sonoga-

shira: PdCl₂(PPh₃)₂, CuI, Et₃N, THF, 40–60 °C, 16 h; copper-free

Sonogashira: Pd₂(dba)₃, AsPh₃, THF, Et₃N, 60 °C, 16 h.

Scheme 5. Side product formation during the synthesis of trimers.

Sonogashira coupling: PdCl₂(PPh₃)₂, CuI, Et₃N, THF, 40–60 °C,

16 h. Copper-free Sonogashira coupling: Pd₂(dba)₃, AsPh₃THF,

Et₃N, 60 °C, 16 h.

Compound 105 shows that this can be used to prepare

heterobismetallated systems. The bromo precursor for 113

(25%) has been described before.^[6]A comparison of 114

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(29%) with 115 shows that both the 5,10- and 5,15-linkages dimer was the main product and they exhibited good solu-

can easily be achieved. The latter was prepared by reaction bility in organic solvents.

of 68 with 86 in 20% yield.

For the diphenylbutadiyne and butadiyne homocoupled

arrays, Pd-mediated Glaser homocoupling was used.^[37]

However, this method proved less successful with yields of

25 and 35% for dimers 127^[7b]and 129,^[38]respectively. Re-

actions were carried out under dry air and reported results

for these conditions show good yields.^[39]A more oxidative

environment is most likely needed to improve yields but as

these dimers were only used for a mass spectrometry study

further reaction optimization was not carried out. The

other homocoupled dimers 126 and 128 resulted as side

product from the synthesis of 135 and 101, respectively.

Porphyrin oligomers: In order to synthesize the targeted

porphyrin trimers, a dibrominated porphyrin was treated

with a mono-“linker”-substituted porphyrin to form the de-

sired trimer by copper-free Sonogashira coupling. This

method was initially developed by Lindsey and cowork-

ers.^[36a]The free base phenyl-substituted trimers 130 and

131 proved to be quite insoluble in most organic solvents,

although this made their purification easy by filtration

using dichloromethane as the solvent. Any remaining

monomer or other side products were removed and pure

trimers 130 and 131 were obtained in yields of 40 and 32%,

respectively (Scheme 8).

Phenylacetylene- and butadiyne-linked dimers: The phen-

ylacetylene-linked symmetric and unsymmetric dimers were

In order to improve solubility to enable full characteriza-

prepared in a similar manner to dimers 98–116. In general, tions to be carried out and to minimize possible Pd inser-

the copper-free method worked quite well giving 117–125 tion, zinc(II) was introduced into the monomeric porphyrin

in yields of 8–44% (Scheme 7). In these cases the desired core, yielding 132 (26%), with dimer 118 isolated as a side

Scheme 7. Copper-free Sonogashira coupling: Pd₂(dba)₃, THF, Et₃N, 60 °C, 16 h; Pd-Glaser coupling: toluene, Pd(PPh₃)₂Cl₂(0.01 equiv.),

CuI (0.05 equiv.), I₂(0.5 equiv.).

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Unsymmetrical meso-Substituted Porphyrin Dimers and Arrays

product in a yield of 23%. In addition, to improve solubil-

ity, 14 was coupled to 56, producing 134 in a 28% yield.

Although these efforts improved the solubility of the de-

sired product, column chromatographic purification re-

mained problematic. Much streaking was observed as the

trimers were only partially soluble in CH₂Cl₂/hexane and

hence there was an inevitable loss of desired product. In-

creasing the equivalents of palladium(0) catalyst used also

had no positive effect on yields as Pd inserted into the por-

phyrin core and these Pd products appeared as very slow

moving fractions whose presence was determined by mass

spectrometry. Another approach to improve yields was to

introduce different substituents on the porphyrin periphery.

Initially dihexylporphyrin monomers were used, but di-

bromodihexyl 13 is highly insoluble in THF and thus not

appropriate for the copper-free Sonogashira coupling.

Thus, neo-pentyl disubstituted porphyrins 11, 12, 30, 49,

and 55 were chosen as starting materials. Initially, reactions

with these porphyrins gave many side products and UV

data indicated the formation of directly linked oligomers

(see UV section). However, on repeating the reaction using

zinc monomers 49 and 55 followed by purification by pre-

parative TLC, the desired trimer 135 was isolated in a 46%

yield as the main fraction. For the synthesis of 136, full

characterization could not be obtained, although mass

spectrometry results showed its formation. Naphthyl-substi-

Scheme 8. Synthesis of linear trimers. Copper-free Sonogashira

coupling: Pd₂(dba)₃, AsPh₃, THF, Et₃N, 60 °C, 16 h.

Scheme 9. Synthesis of linear trimers. Copper-free Sonogashira

coupling: Pd₂(dba)₃, AsPh₃, THF, Et₃N, 65 °C, 16 h.

Scheme 10. Synthesis of L-shaped trimers. Copper-free Sonoga-

shira coupling: Pd₂(dba)₃, AsPh₃, THF, Et₃N, 65 °C, 16 h.

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tuted trimer 137 exhibited similar solubility problems,

which is reflected in the low coupling yield of 22%.

The reverse strategy, i.e. having a diethynyl central unit

A similar coupling of 143^[6]with 77 gave the ethynyl-

linked trimer 149 in 7% yield.

Lastly, we used tribromo 82 to construct a tetrameric

and reacting it with monobromo side units can also be used porphyrin array with both 5,15 and 5,10 linkages (150). Re-

(Scheme 9). Trimers 140 and 141 were synthesized in yields action of 82 with 29 under copper-free Sonogashira condi-

of 13 and 18%, respectively. These yields are however, lower tions gave 150 in low yield (Scheme 11).

than those observed for the other synthetic strategy.

Side products: A number of side products were isolated

Next we turned our attention to the synthesis of L- during the trimer syntheses (Scheme 5). For the synthesis

shaped trimers, i.e. porphyrin systems with connecting link- of 131, the Glaser-coupled dimer 126 was a side product,

ers in the 5,10-substituent pattern. The synthesis of these perhaps due to trace copper presence and also the dimer

compounds is outlined in Scheme 10. The low yields for side product 118, due to incomplete reaction. For the syn-

trimers 145–148 can again be attributed to solubility prob- thesis of trimers 135 and 136 using Sonogashira conditions,

lems. An attempt to resolve this by the introduction of the bromo dimer side products 151 and 152 proved to be

hexyl substituents, forming 147, had no positive effect on the main products isolated showing an incomplete reaction,

the reaction yield.

with no trimer formation. This suggests that the reaction

conditions are not forceful enough for the trimer to form.

Glaser-coupled 126 was also a side product here due to the

presence of CuI. Addition of more copper/Pd, increasing

the temperature and reaction time gave no improvement on

the outcome, and the trimers were not formed, only more

side products.

NMR Studies

Noteworthy NMR spectra resulted from the analysis of

the oligomers synthesized. Different chemical shift patterns

were observed depending on the linker between the por-

phyrin units (Figure 2).

Figure 2. ¹H NMR spectra of 94, 101, 102, 103, and 134 in CDCl₃

showing β and aryl regions.

With the directly linked dimer 94, a large upfield shift

to approximately 9 ppm of the β protons was observed, in

comparison with the monomeric porphyrins, where the last

set of β signals was observed at approximately 9.8 ppm. In

contrast, the alkyne-linked oligomers exhibited a different

pattern with the deshielded β protons shifted downfield.

Some of these shifts occur at around 10.4 ppm, a shift of

Scheme 11. Synthesis of a porphyrin tetramer. Copper-free Sonoga-

shira coupling: Pd₂(dba)₃, AsPh₃, THF, Et₃N, 65 °C, 5 h.

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Unsymmetrical meso-Substituted Porphyrin Dimers and Arrays

1

Figure 3. H–¹H COSY NMR spectra of trimer 135 in [D₈]THF and unsymmetric dimer 101 in CDCl₃.

approximately 0.7 ppm with respect to the monomeric com- into the 700–800 nm region for some trimers. A strong

ponents. In addition, these β protons exhibit signals over a broad Q-band absorbance intensity was also observed with

wider range than those of the directly linked dimers. With these arrays, in particular for alkyl trimer 135.

the phenylacetylene-linked trimers, a downfield shift was

also observed for the meso and β protons, being more pro-

nounced for the β protons. Using ¹H–¹H COSY NMR

analysis (Figure 3), a correlation between the β and aryl

protons on trimer 134 and dimer 101 was shown. It is inter-

esting to note that with trimer 134, the meso proton signal

overlaps with that of the β signals. In addition, the signals

are quite broad for this alkyl-substituted trimer, most likely

due to aggregation. The overlap was also seen for the alkyl-

substituted monomers 49 and 55, indicating that it is a re-

sult of the substitution pattern on the array and indepen-

dent of the linker.

UV/Vis Spectroscopy

The extension of the porphyrin π-conjugation results in

Figure 4. UV/Vis absorbance spectrum of trimers 132 and 135 vs.

monomers 56 and 55 in CH₂Cl₂. Inset: emission spectrum of trimer

132 vs. monomer 56 excited at 443 nm and trimer 135 vs. monomer

56, excited at 445 nm. Concentration: 1.7ϫ10^–7m in THF.

a decrease of the highest occupied molecular orbital–lowest

unoccupied molecular orbital gap due to the change in the

electron density distribution on the porphyrin.^[15,41]The ab-

sorption spectra of the porphyrin oligomers depend on the

type of linker used and the substituents on the porphyrin

macrocycle. With the porphyrin oligomers, most showed a

significant split in the Soret band,^[42]indicating strong con-

jugation between the porphyrin units, except for the di-

phenylbutadiyne-linked dimers where a small split was seen,

indicating here that the communication between porphyrin

subunits is not very efficient. Likewise, in the case of di-

rectly linked dimers 94–97, a split in the Soret band was

observed due to excitonic coupling,^[2c]but no bathochromic

shift was observed as there is no conjugation between the

units. The dimer behaves like its monomeric component

and thus these systems are not of interest with respect to

PDT and NLO but useful for comparison with the conju-

gated systems. On the other hand, the phenylacetylene-

linked dimers and trimers showed a significant split, in par-

ticular for 135 (Figure 4), which shows that there is efficient

interaction between all porphyrin units in the array.^[41]Ad-

ditionally, in comparison to monomer Q-band values, there

Figure 5. Absorbance spectrum of unsymmetric dimers 100 and

101 vs. monomer 71. Inset: emission spectrum of 100 and 101 ex-

cited at both Soret bands vs. monomer 71. Concentration:

is a large bathochromic shift due to increase in conjugation, 1.7ϫ10^–7m in THF.

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Emission studies also showed a bathochromic shift for Mass Spectrometry

these oligomers compared to their monomeric components.

Mass spectrometry provides a useful tool for the struc-

tural elucidation of porphyrins.^[43]The mass spectrometric

analysis of 118, 127, 132, 136, 151, and 152 gave unusual

results. As shown in Figure 6, the spectra for dimer 127 and

trimer 132 contained signals due to the parent ions of the

compounds at m/z 1250 and 1773, respectively, confirming

the elemental composition. However, the spectra also

showed peaks due to demetallated species, which is not usu-

ally observed. Signals at 1187 and 1124 for dimer 127 and

at 1711, 1647, and 1584 for trimer 132 correspond to se-

quential loss of zinc from the oligomers.

Fragmentation of metalloporphyrins typically proceeds

without loss of the metal ion, except in rare cases.^[44]Studies

utilizing MALDI-TOF mass spectrometry showed loss of

magnesium only for magnesium porphyrins, which are con-

sidered the most labile metalloporphyrins. Studies on zinc

porphyrin arrays, in particular, also show that there is no

significant demetallation of the compounds.^[45]Similar frag-

mentation was observed with dimers 118, 151, and 152.

Note that this demetallation was not observed in the mass

spectra of the butadiyne-linked dimer 121^[38]or trimer 135,

which indicates that demetallation is affected both by the

linker and the substituents on the porphyrin rings. Further-

more, the nickel(II) trimer 133 did not exhibit any loss of

nickel from its core, thereby illustrating that this fragmenta-

tion process is also metal dependent. The purity of all ar-

rays was confirmed by ¹H NMR analysis which shows that

there is no demetallation in the analytes as no inner N–H

signals were observed. This eliminates any possibility that

losses in zinc were due to the presence of partially demetall-

ated products in the analyte.

This is expected due to the increase in π-conjugation, thus

these oligomers are possible leads for applications in NLO

and PDT.

With the unsymmetric alkyne-linked dimers, again there

was a Soret band split and also a significant bathochromic

shift to approximately 730 nm (Figure 5). The split differs

from that of the phenylacetylene-linked arrays due to the

less rigid geometry of the alkyne linker, thus allowing the

dimer to adopt many different conformations. Also, as seen

with the trimeric arrays, the Q-band absorbance of these

dimers was more intense in comparison to the monomers.

Emission spectra exhibited a significant bathochromic shift,

again due to the increase in π-conjugation. Hence, these

unsymmetrical dimeric arrays also have the potential to be

used in optical applications.

NLO Properties

Similar to the concept outlined in ref.^[6], selected dimers

and trimers were investigated with regard to their NLO

properties. Overall, the nonlinear absorption coefficient,

β_eff, of dimers and trimers were in the same range as for

the A₂BC-type monomers. For about 20 dimer and trimers

investigated the range was β_eff= 0.5–2.7ϫ10^–8cmW^–1. A

detailed discussion of these data and comparison with the

monomers has been given.^[13b]

Conclusions

Porphyrin dimers and trimers were synthesized in moder-

ate to good yields using Pd-mediated Glaser coupling reac-

tions and copper-free Sonogashira coupling reactions.

These provide a useful route towards the synthesis of such

oligomers. Introduction of alkyl substituents into the pe-

riphery greatly enhanced the solubility and hence the yields.

The uncapped oligomers with free meso positions allow for

subsequent chemical modifications of the free meso posi-

tions.^[14,46]All dimers and trimers exhibited a redshift in

their UV/Vis absorption and emission spectra compared to

Figure 6. Mass spectra of 127 and 132 showing the loss of zinc

from the porphyrin core.

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Unsymmetrical meso-Substituted Porphyrin Dimers and Arrays

rated and the residue was dissolved in CH₂Cl₂. This mixture was

washed with saturated NaHCO₃, H₂O, and brine and then dried

with Na₂SO₄. The organic solvent was evaporated and the crude

product was purified by flash chromatography followed by

recrystallization from CH₂Cl₂/MeOH.

the monomers. In particular, the alkyne-linked dimers

showed strong absorption around 720 nm, making them

good candidates for use as, e.g. possible photosensitizers in

PDT and in other optical applications. With unsymmetrical

dimers and trimers, amphiphilicity can be enhanced

through alteration of the substitution patterns, and they

also allow for the fine tuning of optical properties, which

would enhance either their PDT or NLO effect. Unsymmet-

rical arrays are advantageous in that they may be con-

structed with both hydrophilic and lipophilic components

for applications in PDT or electron withdrawing and donat-

ing groups can be introduced to enhance NLO effects. In

addition, the mass spectrometry of the phenylacetylene-

and diphenylbutadiyne-linked oligomers exhibited an un-

usual demetallation pattern for the zinc(II) compounds.

This new fragmentation process is metal and substituent

dependent.

General Procedure E. Suzuki Coupling for the Synthesis of Directly

Linked Dimers: A Schlenk tube was charged with bromoporphyrin

(1 equiv.), porphyrinyl boronate (1 equiv.), and Cs₂CO₃(1.5 equiv.)

and dried under high vacuum. Dry DMF (1 mL) and dry toluene

(2 mL) were added, and the mixture was degassed by three freeze-

pump-thaw cycles. Pd(PPh₃)₄(0.2 equiv.) was added, and the flask

sealed and stirred at 80 °C. The reaction was followed by TLC.

Once the starting material was consumed, the reaction was

quenched with water and extracted into CH₂Cl₂. The organic layer

was dried with MgSO₄, evaporated to dryness, and subjected to

column chromatography.

General Procedure F. Preparation of Ethyne Porphyrins by Sonoga-

shira Coupling: Bromoporphyrin (1 equiv.), PdCl₂(PPh₃)₂

(0.2 equiv.) and CuI (0.3 equiv.) were added to a Schlenk flask and

dried under high vacuum. The vacuum was released under argon

to allow the addition of triethylamine (40 mL) and THF (10 mL).

Argon was bubbled through the stirring solution for 10 min to de-

oxygenate. Trimethylsilylacetylene (10 equiv.) was added, and the

flask was sealed and allowed to stir at room temperature. The reac-

tion was followed by TLC using CHCl₃/hexane (1:2, v/v). Once the

starting material was consumed, the solvent was removed in vacuo

and the residue was dry loaded onto silica using CHCl₃/hexane

(1:3, v/v) as an eluent. The desired compound was collected and

recrystallized using CH₂Cl₂/MeOH.

Experimental Section

General Methods: Solvents used, preparation of starting materials,

spectroscopic instrumentation, and analyses were performed as de-

scribed in Ref.^[6]

General Procedure A – Bromination of Porphyrins: This procedure

was adapted from Boyle and coworkers.^[19a]Porphyrin (1 equiv.)

was dissolved in CHCl₃and NBS (0.8–2.1 equiv.) and pyridine

(0.1 mL) were added. The reaction progress was monitored by TLC

using chloroform/hexane (1:1). The reaction was stopped when all

the starting material was consumed. The mixture was filtered

through a silica gel plug and recrystallized using CH₂Cl₂/MeOH.

General Procedure G. Sonogashira Reaction: A degassed solution

of triethylamine (15 mL) and THF (5 mL) was cooled to 0 °C. Por-

phyrin (1 equiv.), alkynyl substrate, CuI, and Pd(PPh₃)₂Cl₂were

added. After 10 min, the cold bath was removed and the reaction

mixture was stirred for an additional 2–5 h. The reaction mixture

was filtered through silica gel. The solvent was evaporated and the

crude product was purified by flash column chromatography and

recrystallization from CH₂Cl₂/MeOH.

General Procedure B. Zinc(II) Insertion: Adapting a method by

Buchler,^[28]porphyrin (1 equiv.) was dissolved in CHCl₃(25–

50 mL) and heated to reflux for 10 min. Zinc(II) acetate (5 equiv.)

in MeOH (1 mL) was added and the reaction heated to reflux for

30 min. On completion of the reaction, solvents were removed in

vacuo and the residue was redissolved in CH₂Cl₂. This solution

was passed through a plug of silica using CH₂Cl₂as eluent. Sol-

vents were removed in vacuo to give a pink/purple solid followed

by recrystallization from CH₂Cl₂/MeOH.

General Procedure H. Deprotection of Trimethylsilylalkynylpor-

phyrins: Trimethylsilylethynylporphyrin (1 equiv.) was dissolved in

CH₂Cl₂and TBAF (1 m, 1 mL) was added. The reaction was fol-

lowed by TLC using CH₂Cl₂/hexane (1:1, v/v). Upon completion,

the solution was filtered through a plug of silica using CH₂Cl₂as

eluent. Solvent was removed in vacuo and the residue recrystallized

using CHCl₃/MeOH.

General Procedure C. Borylation of Haloporphyrins: The borylation

of haloporphyrins was carried out by adapting a procedure by Fu-

kuzumi and coworkers.^[34]Bromoporphyrin (1 equiv.) and

Pd(PPh₃)₄(0.2 equiv.) were added to a Schlenk flask and dried un-

der high vacuum. 1,2-Dichloroethane (10 mL) and NEt₃(180 μL)

were added and the solution was degassed by three freeze-pump-

thaw cycles, before the flask was purged with argon. Pinacolborane

(15 equiv.) was added and the flask was sealed and stirred at 90 °C.

The reaction was followed by TLC using CH₂Cl₂/hexane (2:1, v/v).

Once the starting material was consumed, the reaction was

quenched with saturated KCl solution (10 mL), washed with water,

and dried with MgSO₄. The solvent was removed in vacuo and the

residue was subjected to column chromatography using CH₂Cl₂/

hexane (1:1).

General Procedure I. Reaction with Organolithium Reagents: The

porphyrin was dissolved in dry THF (80 mL) under an argon atmo-

sphere and the reaction mixture was cooled to –78 °C. nBuLi

(6 equiv.) was added dropwise over 15 min by syringe. The cold

bath was removed and stirring continued 1.5 h at room tempera-

ture. Water (0.5 mL) was added and stirring continued for 15 min.

2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 6 equiv.) was

added in THF (10 mL) and the reaction mixture was stirred for an

additional hour. The reaction mixture was filtered through silica

gel, followed by evaporation of the solvent. The crude reaction mix-

ture was purified by column chromatography.

General Procedure D. Suzuki Coupling: A Schlenk flask was

charged with K₃PO₄(20 equiv.) and anhydrous THF (60 mL) un-

der an argon atmosphere. Porphyrin (1 equiv.), arylboronic acid or

arylboronic ester (10 equiv.), and Pd(PPh₃)₄(0.1 equiv.) were

added. The reaction was heated to reflux for 7–10 h (TLC control)

and protected from light. After completion, the solvent was evapo-

General Procedure J. Copper-Free Sonogashira Coupling of Por-

phyrin Dimers: This procedure was adapted from a method by

Wagner et al.^[36a]Bromoporphyrin (1 equiv.), ethynylporphyrin

(1 equiv.), Pd₂(dba)₃(0.4 equiv.), and AsPh₃(1 equiv.) were added

to a Schlenk tube and dried under high vacuum. The flask was

purged with argon and dry THF (10 mL) and NEt₃(1 mL) were

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M. O. Senge et al.

FULL PAPER

added. Argon was bubbled through the stirring solution for 10 min

to deoxygenate it. The flask was sealed, and the reaction mixture

heated to 65 °C. The reaction was followed by TLC using CH₂Cl₂/

hexane (1:1, v/v). Once the starting material was consumed, the

solvent was removed and the residue dry loaded onto silica.

146.6, 148.6, 150.5 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 421 (5.86),

486 (4.39), 557 (4.52), 659 nm (4.42) ppm. HRMS (ESI) m/z calcd.

for C₅₄H₆₆BrN₄[M + H]⁺849.4471; found 849.4436.

5-Bromo-15-(3-methoxyphenyl)-10,20-diphenylporphyrin (19): Pro-

duced from 36 (100 mg, 0.176 mmol) and NBS (47 mg,

0.263 mmol) in CHCl₃(60 mL) following general procedure A to

give purple product 19 (110 mg, 97%); m.p. Ͼ 300 °C. ¹H NMR

(400 MHz, CDCl₃, TMS): δ = –2.74 (s, 2 H, NH) 4.00 (s, 3 H,

OCH₃), 7.34–7.36 (m, 1 H, p-PhOMe-H), 7.66 (m, 1 H, m-PhOMe-

General Procedure K. Copper-Free Sonogashira Coupling for Por-

phyrin Arrays: This procedure was adapted from a method by

Wagner et al.^[36a]For the synthesis of dimers 117–125 a 1:1 ratio of

phenylethynylporphyrin/monobromoporphyrin was used. For the

trimers 130–137, monofunctionalized porphyrin (2.1 equiv.) and di-

functionalized porphyrin (1 equiv.) were added to a Schlenk tube.

To this AsPh₃(2.1 equiv.) and Pd₂(dba)₃were added and the con-

tents dried under high vacuum for 30 min and the flask was purged

with argon. Dry THF (12 mL) and dry triethylamine (4 mL) were

added and the solution was degassed by three freeze-pump-thaw

cycles. The flask was purged with argon, stirred, sealed, heated to

67 °C, and left to stir overnight. The reaction was monitored by

TLC analysis using CH₂Cl₂/n-hexane (1:1, v/v) as eluent. On con-

sumption of starting materials the heat source was removed and

the solvents removed in vacuo. The crude mixture was passed

through a silica plug and the solvents removed in vacuo. Column

chromatography was carried out using different eluents to yield the

desired oligomer.

3

H) 7.76 (m, 8 H, Ph-H), 8.21–8.23 (d, J_H,H= 7.5 Hz, 4 H, Ph-H)

3

8.81–8.83 (d, J_H,H= 4.4 Hz, 2 H, H_β), 8.87–8.88 (d, J_H,H

=

4.3 Hz, 2 H, H_β), 8.92–8.93 (d, ³J_H,H= 4.4 Hz, 2 H, H_β), 9.69–9.71

(d, J_H,H= 4.7 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃):

3

δ = 55.3, 102.8, 113.5, 120.3, 130.5, 120.6, 126.6, 127.7, 134.4,

141.6, 143.0, 157.9 ppm. UV/Vis (THF): λ_max(logε) = 419 (5.46),

517 (4.09), 550 (3.81), 595 (3.64), 655 nm (3.77) ppm. HRMS

(MALDI) m/z calcd. for C₃₉H₂₇BrON₄[M]⁺646.1368; found

646.1368.

5-Bromo-10,15,20-tris(3-methoxyphenyl)porphyrin (21): Produced

from 38 (157 mg, 0.25 mmol) and NBS (93 mg, 0.52 mmol) follow-

ing general procedure A, purple crystals of 21 were isolated

1

(122 mg, 0.172 mmol, 69%); m.p. Ͼ 300 °C. H NMR (400 MHz,

CDCl₃, TMS): δ = –2.75 (s, 2 H, NH), 4.00 (s, 3 H, OCH₃), 4.02

(s, 6 H, OCH₃), 7.36 (m, 4 H, Ph-H), 7.67 (m, 4 H, Ph-H), 7.79

5,15-Dibromo-10,20-bis(1-ethylpropyl)porphyrin (11): Produced

from 3 (300 mg, 0.493 mmol) and NBS (184 mg, 1.036 mmol) fol-

lowing general procedure A to yield purple product 11 (356 mg,

0.585 mmol, 88%); m.p. Ͼ 300 °C. ¹H NMR (400 MHz, CDCl₃,

TMS): δ = –2.34 (s, 2 H, NH), 0.97 (t, ³J_H,H= 9.9 Hz, 12 H, CH₃),

2.81 (m, 4 H, CH₂), 2.89 (m, 4 H, CH₂), 4.92 (m, 2 H, CH), 9.57

3

(m, 4 H, Ph-H), 8.86 (s, 4 H, H_β), 8.97 (d, J_H,H= 4.5 Hz, 2 H,

3

H_β), 9.69 (d, J_H,H= 4.8 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz,

CDCl₃): δ = 55.4, 55.5, 102.9, 113.6, 113.7, 120.4, 120.5, 120.6,

127.5, 127.6, 127.7, 131.9, 143.1, 143.2, 158.0 ppm. UV/Vis

(CH₂Cl₂): λ_max(logε) = 421 (5.46), 517 (4.11), 553 (3.76), 595

(3.57), 652 nm (3.47) ppm. HRMS (ESI) m/z calcd. for

C₄₁H₃₁BrN₄O₃[M + H]⁺707.1658; found 707.1655.

3

(d, J_H,H= 2.9 Hz, 4 H, H_β), 9.75 (d, J_H,H= 3.2 Hz, 4 H, H_β)

ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 13.8, 24.4, 34.4, 50.0, 67.0,

124.4, 129.8, 133.1 ppm. UV/Vis (THF): λ_max(logε) = 422 (5.55),

524 (4.16), 558 (4.05), 606 (3.60), 664 nm (3.84) ppm. HRMS

(MALDI) m/z calcd. for C₃₀H₃₃N₄Br₂[M + H]⁺607.1072 found

607.1066.

5-Bromo-10,15,20-tris(4-methoxyphenyl)porphyrin (22): Following

general procedure A, 22 was produced from 40 (164 mg,

0.26 mmol) and NBS (70 mg, 0.39 mmol). Purple crystals were iso-

lated (112 mg, 0.159 mmol, 61%); m.p. Ͼ 300 °C. ¹H NMR

(400 MHz, CDCl₃, TMS): δ = –2.74 (s, 2 H, NH), 4.09 (s, 3 H,

5-Bromo-10,20-bis(1-ethylpropyl)porphyrin (12): Produced from 3

(300 mg, 0.665 mmol) and NBS (95 mg, 0.532 mmol) in CHCl₃

(250 mL) following general procedure A to yield purple product 12

3

OCH₃), 4.11 (s, 6 H, OCH₃), 7.30 (d, J_H,H= 8.6 Hz, 6 H, Ph-H),

3

8.09 (m, 6 H, Ph-H), 8.82 (s, 4 H, H_β), 8.92 (d, J_H,H= 4.6 Hz, 2

3

1

H, H_β), 9.66 (d, J_H,H= 4.8 Hz, 2 H, H_β) ppm. ¹³C NMR

(190 mg, 0.358 mmol, 54%); m.p. Ͼ 300 °C. H NMR (400 MHz,

3

(150 MHz, CDCl₃): δ = 55.4, 55.5, 102.4, 112.2, 120.3, 120.7, 120.5,

134.1, 134.2, 135.2, 135.4, 135.5, 159.3, 159.4 ppm. UV/Vis

(CH₂Cl₂): λ_max(logε) = 423 (5.56), 522 (4.20), 556 (4.02), 599

(3.71), 655 nm (3.81) ppm. HRMS (ESI) m/z calcd. for

C₄₁H₃₁BrN₄O₃[M]⁺707.1658; found 707.1671.

CDCl₃, TMS): δ = –2.48 (s, 2 H, NH), 0.96 (t, J_H–H= 14.6 Hz, 3

H, CH₃), 2.82 (m, 4 H, CH₂), 3.05 (m, 4 H, CH₂), 5.00 (m, 2 H,

3

CH), 9.34–9.35 (d, J_H,H= 3.1 Hz, 2 H, H_β), 9.66 (m, 4 H, H_β),

3

9.87 (d, J_H,H= 3.4 Hz, 4 H, H_β), 10.11 (s, 1 H_,H_meso) ppm. ¹³C

NMR (150 MHz, CDCl₃): δ = 13.9, 14.0, 34.7, 50.4, 77.2, 124.8,

132.7 ppm. UV/Vis: λ_max(logε) = 414 (5.44), 514 (4.14), 546 (3.64),

592 (3.54), 648 nm (3.42) ppm. HRMS (MALDI) m/z calcd. for

C₃₀H₃₄N₄Br [M + H]⁺529.1967; found 529.1967.

5-Bromo-15-butyl-10,20-bis(4-methoxyphenyl)porphyrin (23): Pro-

duced from 41 (79 mg, 0.13 mmol) and NBS (46 mg, 0.26 mmol)

using general procedure A. Purple crystals were isolated (50 mg,

0.070 mmol, 55%); m.p. Ͼ 300 °C. ¹H NMR (400 MHz, CDCl₃,

5-Bromo-10,20-bis(3,5-di-tert-butylphenyl)-15-hexylporphyrin (16):

Produced from 33 (75 mg, 0.097 mmol) and NBS (20 mg,

0.112 mmol) in CHCl₃(150 mL) following general procedure A.

After 50 min the solvent was removed in vacuo and the residue

purified by column chromatography (silica, CH₂Cl₂/hexane, 1:2) to

yield a purple solid; yyield 75 mg (0.088 mmol, 91%); m.p. Ͼ

300 °C. ¹H NMR (400 MHz, CDCl₃, TMS): δ = –2.64 (s, 2 H,

NH), 0.94–0.98 (t, ³J_H,H= 14.5 Hz, 3 H, CH₃), 1.41 (m, 2 H, CH₂),

1.57 (s, 36 H, tert-butyl-H), 1.66 (m, 2 H, CH₂), 1.86 (m, 2 H,

CH₂), 2.57 (m, 2 H, CH₂), 4.99 (m, 2 H, CH₂), 7.85 (m, 2 H, Ph-

3

TMS): δ = –2.70 (s, 2 H, NH) 1.12 (t, J_H,H= 7.34 Hz, 3 H, 5-

CH₃), 1.80 (m, 2 H, 3-CH₂), 2.50 (m, 2 H, 2-CH₂), 4.12 (s, 6 H,

3

OCH₃), 4.97 (m, 2 H, 1-CH₂), 7.30 (d, J_H,H= 8.43 Hz, 5 H, Ph-

3

H), 8.09 (d, J_H,H= 8.34 Hz, 5 H, Ph-H), 8.88 (m, 4 H, H_β), 9.44

3

(d, J_H,H= 4.7 Hz, 2 H, H_β), 9.59 (d, J_H,H= 4.9 Hz, 2 H, H_β)

ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 14.2, 23.6, 35.3, 40.8, 55.5,

55.6, 101.8, 112.2, 119.9, 121.5, 134.4, 135.4, 135.5, 159.5 ppm.

UV/Vis (CH₂Cl₂): λ_max(logε) = 423 (5.33), 522 (4.01), 557 (3.79),

600 (3.45), 656 nm (3.57) ppm. HRMS (ESI) m/z calcd. for

C₃₈H₃₃BrN₄O₂[M + H]⁺657.1865; found 657.1854.

3

H), 8.05–8.07 (d, J_H,H= 1.5 Hz, 4 H, Ph-H), 8.92 (m, 4 H, H_β),

3

9.46–9.47 (d, J_H,H= 4.8 Hz, 2 H, H_β), 9.62–9.63 (d, J_H,H

=

5-Bromo-15-(4-ethynylphenyl)-10,20-diphenylporphyrin (24): Fol-

4.8 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 13.5, lowing general procedure A, 29 (100 mg, 0.177 mmol) and NBS

20.9, 30.2, 34.9, 35.2, 38.7, 101.5, 121.0, 121.3, 121.4, 123.5, 124.7,

127.7, 128.3, 128.6, 128.7, 129.6, 134.2, 138.9, 140.9, 144.0, 146.5,

(33 mg, 0.186 mmol) gave 105 mg (0.16 mmol, 92%) of a purple

solid after recrystallization from CH₂Cl₂/MeOH; M.p. Ͼ300 °C; R_f

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Unsymmetrical meso-Substituted Porphyrin Dimers and Arrays

1

= 0.2 (CH₂Cl₂/n-hexane = 1:1, v/v). H NMR (400 MHz, CDCl₃, column chromatography (CH₂Cl₂/hexane, 1:6, v/v) to yield two

TMS): δ = –2.74 (s, 2 H, NH), 3.34 (s, 1 H, CϵCH), 7.81 (m, 6 H, fractions, the starting material 2 and the desired product 31, which

3

Ar-H), 7.91 (d, ³J = 7.6 Hz, 2 H, Ar-H), 8.17 (d, J = 7.6 Hz, 2 H,

gave purple crystals upon recrystallization from CH₂Cl₂/MeOH

(72 mg, 0.125 mmol, 30%); m.p. Ͼ 300 °C. ¹H NMR (400 MHz,

CDCl₃, TMS): δ = –2.84 (s, 2 H, NH), 0.90–0.92 (t, 6 H, CH₃),1.42

(m, 4 H, CH₂), 1.53 (m, 4 H, CH₂), 2.55 (m, 4 H, CH₂), 3.36 (s, 1

3

Ar-H), 8.21 (d, J = 7.1 Hz, 4 H, Ar-H), 8.82 (m, 4 H, H_β), 8.93

(d, J = 4.1 Hz, 2 H, H_β), 9.70 (d, J = 4.7 Hz, 2 H, H_β) ppm. ¹³C

NMR (150 MHz, CDCl₃): δ = 83.6, 103.2, 119.8, 120.9, 121.8,

126.7, 127.9, 130.6, 134.5, 141.7, 142.5 ppm. UV/Vis (CH₂Cl₂):

3

H, CϵCH), 5.01 (m, 4 H, CH), 7.91–7.93 (d, J_H,H= 6.4 Hz, 2 H,

3

λ_max(logε) = 420 (4.87), 518 (3.45), 555 (3.13), 598 (2.69), 651 nm C₆H₄-H), 8.18–8.19 (d, J_H,H= 6.2 Hz, 2 H, C₆H₄-H), 8.89 (s, 2

(2.57) ppm. HRMS (MS ES⁺) m/z calcd. for [C₄₀H₂₆N₄Br] [M +

H, H_β), 9.40 (s, 2 H, H_β), 9.48 (s, 2 H, H_β), 9.59 (s, 2 H, H_β), 10.11

(s, 1 H, H_meso) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 14.0, 25.6,

29.6, 30.1, 34.8, 38.5, 78.0, 83.7, 118.0, 119.4, 121.3, 127.4, 128.0,

130.1, 131.4, 131.6, 134.2, 143.7, 144.7, 147.2 ppm. UV/Vis (THF):

λ_max(logε) = 411 (5.43), 511 (4.12), 542 (3.54), 592 (3.38), 644 nm

(3.19) ppm. HRMS (ESI) m/z calcd. for C₄₀H₄₃N₄[M + H]⁺

579.3488; found 579.3463.

H⁺]: 641.1341; found 641.1343.

5-Bromo-15-(4-nitrophenyl)-10,20-diphenylporphyrin (25): Follow-

ing general procedure A, 57 (100 mg, 0.171 mmol) and NBS

(32 mg, 0.179 mmol) gave 105 mg (0.16 mmol, 92%) of a purple

solid after recrystallization from CH₂Cl₂/MeOH; m.p. Ͼ300 °C; R_f

= 0.24 (CH₂Cl₂/n-hexane = 1:1, v/v). H NMR (400 MHz, CDCl₃,

TMS): δ = –2.73 (s, 2 H, NH), 7.82 (m, 6 H, Ar-H), 8.21 (d, J =

1

3

5,15-Bis(3,5-di-tert-butylphenyl)-10-hexylporphyrin (33): Com-

pound 4 (100 mg, 0.145 mmol) was dissolved in THF (40 mL) and

cooled to –78 °C. n-Hexyllithium (2.5 m in hexane, 1.0 mL,

2.5 mmol) was added dropwise over 30 min. After addition, the

solution was stirred for 15 min at –78 °C before warming to room

temperature. H₂O/THF (1:1, 5 mL) was added and stirring contin-

ued for 10 min. DDQ (329 mg, 1.45 mmol) was added and the solu-

tion stirred for 20 min. All solvents were removed, the brown resi-

due dissolved in CH₂Cl₂(20 mL) and filtered through a plug of

silica. The purple solution was purified by column chromatography

(silica, CH₂Cl₂/hexane, 1:2, v/v) to yield a purple solid; yyield

3

7.0 Hz, 4 H, Ar-H), 8.38 (d, J = 8.8 Hz, 2 H, Ar-H), 8.65 (d, J

3

= 8.2 Hz, 2 H, Ar-H), 8.72 (d, J = 4.1 Hz, 2 H, H_β), 8.87 (d, J =

4.7 Hz, 2 H, H_β), 8.94 (d, ³J = 4.7 Hz, 2 H, H_β), 9.71 (d, ³J =

4.7 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 103.7,

104.1, 107.9, 117.3, 121.1, 121.8, 126.7, 127.9, 132.1, 134.4, 134.8,

141.3, 147.7, 148.7 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 421 (4.98),

518 (3.75), 555 (3.57), 599 (3.35), 651 nm (3.33) ppm. HRMS (MS

ES⁺) m/z calcd. for [C₃₈H₂₅N₅O₂Br] [M + H⁺]: 662.1192; found

662.1179.

5,15-Bis(1-ethylpropyl)-10-(4-ethynylphenyl)porphyrin

(30):

A

1

84.1 mg (0.109 mmol, 75%); m.p. Ͼ 300 °C. H NMR (400 MHz,

100 mL Schlenk flask containing p-bromophenylethyne (0.91 g,

5.0 mmol) was dried under high vacuum and purged with argon.

Dry diethyl ether (10 mL) was added to this solution and it was

cooled down to –70 °C using a cold bath. nBuLi (4 mL of a 2.5 m

solution in n-hexane, 10 mmol) was added dropwise to the flask

over a period of one hour. The reaction mixture was then warmed

to –40 °C and dry THF was added dropwise until a white-pink

suspension formed. A solution of 3 (200 mg, 0.43 mmol) in dry

THF (80 mL) was added rapidly to the vigorously stirring reaction

mixture under argon. The reaction was left to stir for approximately

16 h, forming a brown solution. Saturated NH₄Cl (2 mL) was

added and the solution turned bright green. DDQ was added and

the solution turned red and was left to stir for a further hour. The

crude mixture was then filtered through a silica plug using CH₂Cl₂

as eluent. Solvents were removed in vacuo and crude residue sub-

jected to column chromatography using CH₂Cl₂/hexane (1:7, v/v)

as eluent. Three fractions were obtained, the first was 3, the second

was the desired product 30, and the third was an inseparable mix-

ture of mono- and disubstituted butylated 3. Recrystallization of 30

from CH₂Cl₂/MeOH yielded purple crystals (86 mg, 0.156 mmol,

35%); m.p. Ͼ 300 °C. ¹H NMR (400 MHz, CDCl₃, TMS): δ =

–2.46 (s, 2 H, NH), 0.96–1.00 (t, 12 H, CH₃), 2.83 (m, 4 H, CH₂),

2.97 (m, 4 H, CH₂), 3.37 (s, 1 H, CϵCH), 5.05 (m, 2 H, CH), 7.90–

CDCl₃, TMS): δ = –2.91 (s, 2 H, NH), 0.94–1.00 (t, 3 H, CH₃),

1.49 (m, 4 H, CH₂), 1.60 (s, 36 H, tert-butyl-H), 1.88 (m, 2 H,

CH₂), 2.63 (m, 2 H, CH₂), 5.13 (m, 2 H, CH₂), 7.82 (m, 2 H, Ar-

H), 8.14 (m, 4 H, Ar-H), 9.04–9.08 (dd, ³J_H,H= 12.3 Hz, 4 H, H_β),

3

9.30–9.31 (d, J_H,H= 4.7 Hz, 2 H, H_β), 9.59–9.60 (d, J_H,H

=

4.7 Hz, 2 H, H_β), 10.13 (s, 1 H, H_meso) ppm. ¹³C NMR (150 MHz,

CDCl₃): δ = 13.9, 14.0, 30.2, 30.3, 34.9, 35.2, 121.1, 121.3, 128.6,

128.7, 128.9, 129.6, 134.2, 138.9, 140.8, 140.9, 144.0, 145.3, 146.5,

148.6, 148.7, 150.5 ppm. UV/Vis (THF): λ_max(logε) = 413 (5.48),

510 (4.04), 544 (3.62), 588 (3.63), 644 nm (3.70) ppm. HRMS (ESI)

m/z calcd. for C₉₄H₈₂N₈[M + H]⁺771.5366; found 771.5360.

5,15-Diphenyl-10-(3-methoxyphenyl)porphyrin

(36):

nBuLi

(12.97 mmol, 5.2 mL) was added slowly to a cooled (0 °C) solution

of 3-bromoanisole (12.97 mmol, 1.64 mL) in freshly distilled diethyl

ether (8 mL). After the addition was complete the reaction mixture

was warmed to room temperature. This mixture was then transfer-

red to a cooled (–20 °C) solution of 1 (1.08 mmol, 500 mg), in

freshly distilled THF (20 mL). The suspension was warmed to

room temperature and stirred for 19 h. Water (6 mL) was added

carefully and after 30 min DDQ (5.40 mmol, 1.23 g) was added.

The mixture continued to stir for 1.5 h after which time the suspen-

sion was passed through a short column of silica gel and the prod-

uct mixture was eluted with DCM. The solvents were removed un-

der reduced pressure and the residue was purified using silica gel

column chromatography (hexane/CH₂Cl₂, 1:1, v/v) to give purple

solid after removal of solvents; yyield (187 mg, 0.329 mmol, 30%);

3

7.92 (d, J_H,H= 5.2 Hz, 2 H, Ph-H), 8.19–8.20 (d, J_H,H= 5.2 Hz,

3

2 H, Ph-H), 8.85–8.86 (d, J_H,H= 2.2 Hz, 2 H, H_β), 9.39–9.40 (d,

3

³J_H,H= 2.2 Hz, 2 H, H_β), 9.59–9.60 (d, J_H,H= 4.8 Hz, 2 H, H_β),

3

9.69–9.71 (d, J_H,H= 8.1 Hz, 2 H, H_β), 10.16 (s, 1 H, H_meso) ppm.

¹³C NMR (150 MHz, CDCl₃): δ = 13.9, 29.6, 34.4, 49.8, 77.9, 83.7,

121.3, 122.5, 129.9, 131.4, 131.7, 134.0, 144.4 ppm. UV/Vis

(CH₂Cl₂): λ_max(logε) = 410 (5.51), 510 (4.26), 542 (3.70), 588

(3.66), 644 nm (3.38) ppm. HRMS (ESI) m/z calcd. for C₃₈H₃₉N₄

[M + H]⁺551.3175; found 551.3170.

1

m.p. Ͼ 300 °C. H NMR (400 MHz, CDCl₃, TMS): δ = –2.97 (s,

2 H, NH), 4.01 (s, 3 H, OCH₃), 7.35–7.38 (m, 1 H, p-PhOCH₃),

3

7.65–7.69 (t, J_H,H= 15.6 Hz, 1 H, m-PhOCH₃), 7.83 (m, 8 H, Ph-

H), 8.28 (m, 4 H, Ph-H), 8.93–8.96 (m, 4 H, H_β), 9.04–9.05 (d,

3

³J_H,H= 4.6 Hz, 2 H, H_β), 9.36–9.38 (d, J_H,H= 4.6 Hz, 2 H, H_β)

5-(4-Ethynylphenyl)-10,20-dihexylporphyrin (31): Following the pro-

cedure given for 30, using p-bromophenylethyne (0.91 g, 5.0 mmol),

nBuLi (4 mL of a 2.5 m solution in n-hexane, 10 mmol) and 2

(200 mg, 0.418 mmol), the desired product was isolated following

10.26 (s, 1 H, H_meso) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 13.7,

21.3, 22.2, 28.9, 29.3, 31.1, 31.5, 55.0, 104.4, 113.1, 119.2, 119.7,

120.0, 126.4, 126.9, 127.3, 130.3, 131.0, 134.3, 141.3, 143.4, 146.7,

157.4 ppm. UV/Vis (THF): λ_max(logε) = 411 (5.65), 508 (4.20),

Eur. J. Org. Chem. 2011, 5817–5844

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5829

M. O. Senge et al.

FULL PAPER

541 (3.44), 581 (3.77), 640 nm (3.50). HRMS (ESI) m/z calcd. for

0.031 mmol, 4%); m.p. Ͼ 300 °C. ¹H NMR (400 MHz, CDCl₃,

TMS): δ = –2.77 (s, 2 H, NH), 4.01 (s, 6 H, OCH₃), 7.34–7.35 (d,

C₃₉H₂₉N₄O [M]⁺568.2263; found 568.2254.

3

³J_H,H= 2.3 Hz, 1 H, p-PhOCH₃), 7.36–7.37 (d, J_H,H= 2.4 Hz, 1

5,10,20-Tris(4-methoxyphenyl)porphyrin (40): nBuLi (12.97 mmol,

5.2 mL) was added slowly to a cooled (0 °C) solution of 3-bromo-

anisole (12.97 mmol, 1.64 mL) in freshly distilled diethyl ether

(8 mL). After the addition was complete the reaction mixture was

warmed to room temperature. This mixture was then transferred

to a cooled (–20 °C) solution of 6 (1.08 mmol, 500 mg) in freshly

distilled THF (20 mL). The suspension was warmed to room tem-

perature and stirred for 19 h. Water (6 mL) was added carefully

and after 30 min DDQ (5.40 mmol, 1.23 g) was added. The mixture

continued to stir for 1.5 h after which time the suspension was

passed through a short column of silica gel and the product mixture

was eluted with CH₂Cl₂. The solvents were removed under reduced

pressure and the residue was purified using silica gel column

chromatography (hexane/CH₂Cl₂, 1:1, v/v) to give purple solid 40

after removal of solvents (187 mg, 0.297 mmol, 31%). ¹H NMR

3

H, p-PhOCH₃), 7.65–7.69 (t, J_H,H= 15.2 Hz, 2 H, m-PhOCH₃),

7.79 (m, 10 H, Ph-H), 8.24–8.25 (d, ³J_H,H= 5.8 Hz, 4 H, o-Ph–H),

3

8.86–8.87 (d, J_H,H= 4.6 Hz, 4 H, H_β), 8.91–8.92 (d, J_H,H

=

4.7 Hz, 4 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 55.3,

55.8, 113.6, 115.6, 120.3, 122.2, 122.4, 124.2, 126.5, 127.3, 127.7,

127.8, 128.2, 128.9, 129.8, 131.7, 134.4, 138.8, 139.7, 143.3, 145.8,

145.9, 157.8, 159.1 ppm. UV/Vis (THF): λ_max(logε) = 417 (5.41),

513 (4.05), 547 (3.73), 588 (3.71), 647 nm (3.66). HRMS (ESI) m/z

calcd. for C₃₉H₂₉N₄O [M + H]⁺675.2760; found 675.2748.

[5,15-Dibromo-10,20-bis(1-ethylpropyl)porphyrinato]zinc(II)

(49):

Produced from 11 (200 mg, 0.329 mmol) dissolved in CHCl₃

(40 mL) and Zn(OAc)₂(301 mg, 1.645 mmol), following general

procedure B to yield pink crystals (194 mg, 0.289 mmol, 88%); m.p.

1

Ͼ 300 °C. H NMR (400 MHz, CDCl₃, TMS): δ = 0.93 (t, 12 H,

(400 MHz, CDCl₃, TMS): δ = –2.99 (br.s, 1 H, NH), 4.04 (m, 6 H,

CH₃), 2.81 (m, 4 H, CH₂), 2.96 (m, 4 H, CH₂), 5.06 (m, 2 H, CH),

3

OCH₃) 4.13 (s, 3 H, OCH₃), 7.37–7.39 (d, J_H–H= 8.5 Hz, 2 H, 9.57 (m, 4 H, H_β), 9.69 (m, 4 H, H_β) ppm. ¹³C NMR (150 MHz,

Ph-H), 7.70 (m, 2 H, Ph-H), 7.83 (m, 4 H, Ph-H), 8.14 (m, 4 H,

CDCl₃): δ = 13.9, 34.4, 50.4, 77.2, 124.8, 131.2 132.7 ppm. UV/Vis

(THF): λ_max(logε) = 428 (5.58), 566 (4.02), 614 nm (3.94). HRMS

(MALDI-TOF) m/z calcd. for C₃₀H₃₀N₄ZnBr₂[M]⁺668.0129;

3

Ph-H), 8.92–8.93 (d, J_H,H= 4.8 Hz, 2 H, H_β), 8.96–8.97 (d, J_H,H

3

= 4.7 Hz, 2 H, H_β), 9.08–9.09 (d, J_H,H= 4.6 Hz, 2 H, H_β), 9.36–

9.37 (d, ³J_H,H= 4.6 Hz, 2 H, H_β), 10.24 (s, 1 H, H_meso) ppm. NMR found 668.0136.

spectroscopic data are in agreement with the literature.^[47]UV/Vis

[5-Bromo-10,20-bis(3,5-di-tert-butylphenyl)-15-hexylporphyrinato]-

(THF): λ_max(logε) = 413 (5.58), 509 (4.14), 544 (3.50), 585 (3.69),

639 nm (3.54). HRMS (MALDI-TOF) m/z calcd. for C₄₁H₃₂O₃N₄

[M]⁺628.2474; found 628.2482.

zinc(II) (51): Produced from 16 (110 mg, 0.132 mmol) dissolved in

CHCl₃(25 mL) and zinc(II) acetate (130 mg, 0.6 mmol) dissolved

in methanol (2 mL) following general procedure B to give a bright

purple solid (106 mg, 0.117 mmol, 90%); m.p. Ͼ 300 °C. ¹H NMR

(600 MHz, CDCl₃, TMS): δ = 1.54 (s, 36 H, tert-butyl-H), 7.81–

5-Butyl-10,20-bis(4-methoxyphenyl)porphyrin 41: This compound

was isolated from the synthesis of 40. It is a side product coming

from the direct reaction of butyllithium with 6, to give a purple

7.83 (m, 2 H, Ph-H), 8.03–8.09 (m, 4 H, Ph-H), 9.02–9.03 (d, ³J_H,H

powder of 41; yield (183 mg, 0.316 mmol, 33%); m.p. Ͼ 300 °C. ¹H = 4.6 Hz, 2 H, H_β), 9.05–9.06 (d, J_H,H= 4.6 Hz, 2 H, H_β), 9.59–

3

NMR (400 MHz, CDCl₃, TMS): δ = –2.99 (br. s, 1 H, NH), 1.14

9.60 (d, J_H,H= 4.7 Hz, 2 H, H_β), 9.74–9.75 (d, J_H,H= 4.6 Hz, 2

H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 14.2, 22.7, 29.7,

30.5, 31.5, 31.8, 39.1, 46.5, 119.4, 120.9, 122.4, 122.5, 123.3, 128.8,

129.1, 129.7, 130.8, 132.4, 132.9, 133.5, 136.8, 141.6, 148.7, 149.7,

150.2, 150.5, 150.6 ppm. UV/Vis (CH₂Cl₂): λ_max(log ε) = 426

(5.62), 557 (4.44), 642 nm (4.12). HRMS (ESI) m/z calcd. for

C₅₄H₆₃BrN₄Zn [M + H]⁺911.3606; found 911. 3769.

3

(d, J_H,H= 7.4 Hz, 3 H, CH₃), 1.87–1.79 (m, 2 H, CH₂), 2.59–2.51

(m, 2 H, CH₂), 4.13 (s, 6 H, OCH₃), 5.14–5.05 (m, 2 H, CH₂), 7.32

3

(d, J_H,H= 8.5 Hz, 3 H, Ph-H), 8.15 (d, J_H,H= 8.5 Hz, 3 H, Ph-

H), 8.99 (t, ³J_H,H= 5.1 Hz, 3 H, H_β), 9.29–9.23 (m, 2 H, H_β), 9.57–

9.52 (m, 2 H, H_β), 10.09 (s, 1 H, H_meso) ppm. ¹³C NMR (150 MHz,

CDCl₃): δ = 14.1, 22.5, 23.8, 29.9, 31.8, 35.6, 41.1, 55.6, 112.4,

118.8, 134.2, 135.6, 135.7, 159.6 ppm. HRMS (ESI) m/z calcd. for

C₄₁H₃₃N₄O₃[M + H]⁺629.2553; found 629.2541.

[5-Bromo-15-hexyl-10,20-diphenylporphyrinato]zinc(II) (53): Pro-

duced from 18^[5d](100 mg, 0.159 mmol) dissolved in CHCl₃

(25 mL) and zinc(II) acetate (170 mg, 0.795 mmol) dissolved in

methanol (2 mL) according to general procedure B to give a purple

5-Butyl-10,20-bis(4-methylphenyl)porphyrin (42): Following general

procedure I, 7 (245 mg, 0.49 mmol), nBuLi (1.19 mL, 2.99 mmol),

H₂O (0.5 mL), and DDQ (445 mg, 1.96 mmol) were used. The solid (92 mg, 0.133 mmol, 84 %); m.p. Ͼ 300 °C. ¹H NMR

3

crude reaction mixture was purified by column chromatography

using n-hexane/ethyl acetate = 20:1 (v/v), and gave the desired prod-

(400 MHz, CDCl₃, TMS): δ = 0.94–0.97 (t, J_H,H= 12.8 Hz, 3 H,

CH₃), 1.40 (m, 2 H, CH₂), 1.51 (m, 2 H, CH₂), 1.82 (m, 2 H, CH₂),

uct (267 mg, 0.44 mmol, 61%) as purple crystals; m.p. Ͼ 300 °C;

2.54 (m, 2 H, CH₂), 4.98 (m, 2 H, CH₂), 7.81 (m, 6 H, Ph-H), 8.19–

1

3

R_f= 0.5 (n-hexane/ethyl acetate = 20:1, v/v). H NMR (400 MHz, 8.21 (d, J_H,H= 7.9 Hz, 4 H, Ph-H), 8.88 (m, 4 H, H_β), 9.46–9.47

3

CDCl₃): δ = 1.18 (t, J_H,H= 7.1 Hz, 3 H, CH₂CH₂CH₂CH₃), 1.90 (d, J_H,H= 3.3 Hz, 2 H, H_β), 9.61–9.62 (d, J_H,H= 3.2 Hz, 2 H,

(m, 2 H, CH₂CH₂CH₂CH₃), 2.60 (m, 2 H, CH₂CH₂CH₂CH₃), 5.13 H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 14.2, 22.8, 29.8, 30.4,

(t, ³J_H,H= 5.3 Hz, 2 H, CH₂CH₂CH₂CH₃), 7.65 (d, ³J_H,H= 8.2 Hz,

31.9, 35.4, 38.9, 120.9, 122.1, 126.6, 127.6, 128.8, 132.3, 132.4,

133.0, 134.5, 142.4, 149.5, 149.6, 149.9 ppm. UV/Vis (CH₂Cl₂):

λ_max(log ε) = 423 (5.33), 557 (3.79), 646 nm (3.57). HRMS

3

4 H, Ar-H), 8.14 (d, J_H,H= 7.6 Hz, 4 H, Ar-H), 9.08 (d, J_H,H

=

3

4.7 Hz, 2 H, H_β), 9.10 (d, J_H,H= 4.7 Hz, 2 H, H_β), 9.39 (d, J_H,H

= 4.7 Hz, 2 H, H_β), 9.69 (d, J_H,H= 4.7 Hz, 2 H, H_β), 10.18 (s, 1 (MALDI-TOF) m/z calcd. for C₃₈H₃₁BrN₄Zn [M]⁺686.1024;

3

H, H_meso) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 14.0, 21.3, 23.6,

35.4, 41.0, 104.8, 119.8, 121.7, 127.9, 128.6, 131.1, 131.9, 132.4,

136.8, 139.2, 149.5, 149.6, 149.7, 149.8 ppm. UV/Vis (CH₂Cl₂):

λ_max(logε) = 415 (5.07), 452 (3.39), 544 nm (3.73). HRMS (MS

ES⁺) m/z calcd. for [C₃₈H₃₂N₄Zn] [M + H⁺]: 608.1891; found

608.1918.

found 686. 1027.

[5-(4-Ethynylphenyl)-10,20-diphenylporphyrinato]nickel(II) (54):

Porphyrin 29^[14a](100 mg, 0.178 mmol) and Ni(acac)₂(49 mg,

0.191 mmol) were dissolved in toluene (75 mL) in a 100 mL flask

and heated to reflux for 3 h. The solvent was removed in vacuo

and product isolated after filtering the redissolved residue through

a plug of silica gel using CH₂Cl₂as eluent. Recrystallization of the

product using CH₂Cl₂/MeOH yielded red-purple crystals (199 mg,

5,15-Bis(3-methoxyphenyl)-10,20-diphenylporphyrin (43): This com-

pound was isolated as a purple powder as a tetrasubstituted side

product from the organolithium synthesis of 36 (21 mg,

1

90%); m.p. Ͼ 300 °C. H NMR (400 MHz, CDCl₃): δ = 3.31 (s, 1

5830

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Eur. J. Org. Chem. 2011, 5817–5844

Unsymmetrical meso-Substituted Porphyrin Dimers and Arrays

3

H, CϵCH), 7.74 (m, 6 H, Ph-H), 7.83–7.85 (d, J_H,H= 7.9 Hz, 2

fied by column chromatography (silica, CH₂Cl_2/hexane, 1:2, v/v) to

3

H, C₆H₄-H), 8.01–8.03 (d, J_H,H= 8.0 Hz, 2 H, C₆H₄-H), 8.05–

8.07 (d, J_H,H= 7.0 Hz, 2 H, Ph-H), 8.77–8.78 (d, J_H,H= 4.8 Hz, NMR (600 MHz, CDCl₃, TMS): δ = –2.32 (s, 2 H, NH), 0.60 [s, 9

yield a purple solid (154 mg, 0.179 mmol, 83%); m.p. Ͼ 300 °C. ¹H

3

2 H, H_β), 8.82–8.83 (d, J_H,H= 5.0 Hz, 2 H, H_β), 8.91–8.92 (d, H, Si(CH₃)₃], 1.54 (s, 36 H, tBuH), 7.76 (m, 3 H, Ph-H), 7.84 (m,

³J_H,H= 4.8 Hz, 2 H, H_β), 9.15–9.16 (d, J_H,H= 4.8 Hz, 2 H, H_β),

2 H, Ar-H), 8.09 (d, J_H,H= 1.5 Hz, 4 H, Ar-H), 8.20–8.21 (d,

3

9.85 (s, 1 H, H_meso) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 83.4,

³J_H,H= 6.6 Hz, 2 H, Ph-H), 8.78–8.79 (d, J_H,H= 4.4 Hz, 2 H,

3

104.6, 118.2, 121.5, 126.7, 127.6, 130.5, 131.6, 132.1, 132.3, 132.5,

H_β), 8.83–8.84 (d, J_H,H= 4.4 Hz, 2 H, H_β), 8.95–8.96 (d, J_H,H=

133.5, 140.7, 141.6, 141.9, 142.7, 142.8 ppm. UV/Vis (THF): λ_max4.4 Hz, 2 H, H_β), 9.69–9.70 (d, J_H,H= 4.4 Hz, 2 H, H_β) ppm. ¹³C

3

(logε) = 407 (5.46), 521 (4.29), 557 nm (3.60). HRMS (MALDI-

NMR (150 MHz, CDCl₃): δ = 31.6, 34.9, 98.5, 101.5, 107.2, 121.0,

121.8, 122.3, 126.6, 127.7, 129.7, 134.1, 140.6, 142.1, 148.8 ppm.

UV/Vis (CH₂Cl₂): λ_max(logε) = 428 (5.12), 529 (3.73), 566 (3.88),

602 (3.35), 663 nm (3.51). HRMS (ESI) m/z calcd. for C₅₉H₆₇N₄Si

[M + H]⁺859.5135; found 859.5145.

TOF) m/z calcd. for C₄₀H₂₄N₄Ni [M]⁺618.1354; found 618.1380.

[5,15-Bis(1-ethylpropyl)-10-(4-ethynylphenyl)porphyrinato]zinc(II)

(55): Produced from 30 (100 mg, 0.181 mmol) dissolved in CHCl₃

and Zn(OAc)₂(166 mg, 0.907 mmol) following general procedure

B to yield purple crystals (90 mg, 0.147 mmol, 81 %); m.p. Ͼ

300 °C. ¹H NMR (400 MHz, CDCl₃, TMS): δ = 0.98–1.02 (t, ³J_H,H

[5,15-Bis(3,5-di-tert-butylphenyl)-10-phenyl-20-(trimethylsilanyl-

ethynyl)porphyrinato]zinc(II) (63): Produced from 50 (50.0 mg,

55.2 μmol), PdCl₂(PPh₃)₂(20.0 mg, 28.6 μmol), CuI (5.0 mg,

26.2 μmol), and ethynyl(trimethyl)silane (0.20 g, 2.04 mmol) fol-

lowing general procedure F. All solvents were removed and the

brown residue purified by column chromatography (silica, CH₂Cl₂/

hexane, 1:3, v/v) to yield a purple solid (23.2 mg, 25.4 μmol, 46%);

= 14.6 Hz, 12 H, CH₃), 2.88 (m, 4 H, CH₂), 3.05 (m, 4 H, CH₂),

3

3.37 (s, 1 H, CϵCH), 5.21 (m, 2 H, CH), 7.94–7.96 (d, J_H,H

=

8.0 Hz, 2 H, Ph-H), 8.24–8.26 (d, ³J_H,H= 6.1 Hz, 2 H, Ph-H), 9.01–

3

9.03 (d, J_H,H= 7.4 Hz, 2 H, H_β), 9.37 (d, J_H,H= 6.9 Hz, 2 H,

H_β), 9.85 (m, 4 H, H_β), 10.19 (s, 1 H, H_meso) ppm. ¹³C NMR

(150 MHz, CDCl₃): δ = 14.2, 29.7, 34.9, 50.5, 77.2, 77.8, 86.5,

123.0, 131.0, 131.3, 131.5, 134.3 ppm. UV/Vis (THF): λ_max(logε)

= 420 (5.73), 554 (4.31), 594 nm (3.64). HRMS (MALDI) m/z

calcd. for C₃₈H₃₇N₄Zn [M + H]⁺613.2310; found 613.2297.

1

m.p. Ͼ 300 °C. H NMR (600 MHz, CDCl₃, TMS): δ = 0.64 [s, 9

H, Si(CH₃)₃], 1.58 (s, 36 H, tBuH), 7.77 (m, 3 H, Ar-H), 7.85 (m,

3

2 H, Ar-H), 8.10–8.11 (d, J_H,H= 1.7 Hz, 4 H, Ph-H), 8.21–8.22

3

(d, J_H,H= 6.8 Hz, 2 H, Ph-H), 8.90–8.91 (d, J_H,H= 4.4 Hz, 2 H,

3

H_β), 8.95–8.96 (d, J_H,H= 4.6 Hz, 2 H, H_β), 9.06–9.07 (d, J_H,H

=

5-(4-Nitrophenyl)-10,20-diphenylporphyrin (57): Following general

procedure D, 9 (150 mg, 0.277 mmol), K₃PO₄(1469 mg,

6.92 mmol), (4-nitrophenyl)boronic acid pinacol ester (862 mg,

3.462 mmol), and Pd(PPh₃)₄(32 mg, 0.028 mmol) gave 138 mg

(0.236 mmol, 85%) of a purple solid after recrystallization from

CH₂Cl₂/MeOH; m.p. Ͼ 300 °C; R_f= 0.42 (CH₂Cl₂/n-hexane = 1:1,

4.6 Hz, 2 H, H_β), 9.80–9.81 (d, J_H,H= 4.5 Hz, 2 H, H_β) ppm. ¹³C

NMR (150 MHz, CDCl₃): δ = 31.7, 35.0, 120.9, 122.7, 123.4, 126.5,

127.5, 129.7, 130.9, 132.1, 133.2, 134.2, 141.4, 148.7, 149.8, 150.3,

150.8, 152.5 ppm. UV/Vis (THF): λ_max(logε) = 433 (5.49), 569

(4.09), 613 nm (4.13). HRMS (MALDI-TOF) m/z calcd. for

C₅₉H₆₄N₄SiZn [M]⁺920.4192; found 920.4191.

3

1

v/v). H NMR (400 MHz, CDCl₃, TMS): δ = –3.00 (s, 2 H, NH),

7.83 (m, 6 H, Ar-H), 8.27 (d, ³J = 7.0, 4 H, 8.8 Hz, Ar-H), 8.42 (d,

³J = 8.2, 2 H, 8.8 Hz, Ar-H), 8.65 (d, ³J = 8.8 Hz, 2 H, Ar-H), 8.79

5,15-Bis(3,5-di-tert-butylphenyl)-10-hexyl-20-(trimethylsilylethynyl)-

porphyrin (64): Following general procedure F, using 15 (65 mg,

0.076 mmol), PdCl₂(PPh₃)₂(20 mg, 0.029 mmol), CuI (10.0 mg,

0.052 mmol), and ethynyl(trimethyl)silane (0.20 g, 2.04 mmol). The

solution was stirred for 20 h at 50 °C. All solvents were removed

and the brown residue purified by column chromatography (silica

gel, CH₂Cl₂/hexane, 1:3, v/v) to yield a purple solid (23 mg,

25.4 μmol, 36 %); m.p. Ͼ 300 °C. ¹H NMR (400 MHz, CDCl₃,

TMS): δ = –2.29 (s, 2 H, NH), 0.61 [s, 9 H, Si(CH₃)₃], 0.94–0.98

3

(d, J = 4.7 Hz, 2 H, H_β), 8.98 (d, J = 4.7 Hz, 2 H, H_β), 9.07 (d,

³J = 4.7 Hz, 2 H, H_β), 9.39 (d, J = 4.7 Hz, 2 H, H_β), 10.29 (s, 1

3

H, H_meso) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 105.2, 116.6,

117.0, 120.7, 120.9, 121.5, 125.4, 126.4, 127.2, 127.6, 130.1, 131.2,

134.7, 141.1, 144.4, 145.4, 146.3, 147.3, 148.5, 149.2 ppm. UV/Vis

(CH₂Cl₂): λ_max(log ε) = 414 (4.88), 511 (3.66), 544 (3.22), 581

(3.23), 637 nm (2.71). HRMS (MS ES⁺) m/z calcd. for

[C₃₈H₂₆N₅O₂] [M + H⁺]: 584.2087; found 584.2093.

3

(t, J_H,H= 14.6 Hz, 3 H, CH₃), 1.43 (m, 4 H, CH₂), 1.57 (s, 36 H,

3

tBuH), 1.85 (m, 2 H, CH₂), 2.56 (m, 2 H, CH₂), 4.99 (t, J_H,H

=

5-(4-Ethynylphenyl)-15-(4-nitrophenyl)-10,20-diphenylporphyrin

(58): Following general procedure D, 24 (100 mg, 0.155 mmol),

K₃PO₄(827 mg, 3.896 mmol), (4-nitrophenyl)boronic acid pinacol

ester (480 mg, 1.93 mmol), and Pd(PPh₃)₄(18 mg, 0.0155 mmol)

gave 35 mg (0.051 mmol, 33%) of a purple solid after recrystalli-

zation from CH₂Cl₂/MeOH; m.p. Ͼ300 °C; R_f= 0.42 (CH₂Cl₂/n-

3

16.4 Hz, 2 H, CH₂), 7.84 (m, 2 H, Ar-H), 8.78–8.81 (d, J_H,H

4.7 Hz, 4 H, Ar-H), 8.90 (m, 4 H, H_β), 9.44–9.45 (d, ³J_H,H= 4.7 Hz,

2 H, H_β), 9.60–9.61 (d, J_H,H= 4.7 Hz, 2 H, H_β) ppm. ¹³C NMR

3

(150 MHz, CDCl₃): δ = 14.4, 22.6, 30.3, 31.6, 34.8, 38.9, 97.6,

101.1, 107.2, 120.9, 121.5, 121.9, 122.5, 129.5, 134.0, 141.0, 148.3,

150.6 ppm. UV/Vis (THF): λ_max(logε) = 424 (5.15), 527 (3.71), 565

(3.78), 607 (3.33), 665 nm (3.53). HRMS (MALDI-TOF) m/z calcd.

for C₅₉H₇₄N₄Si [M]⁺866.5683; found 866.5677.

1

hexane = 1:1, v/v). H NMR (400 MHz, CDCl₃, TMS): δ = –2.77

(s, 2 H, NH), 3.35 (s, 1 H, CϵCH), 7.80 (m, 6 H, Ar-H), 7.93 (d,

³J = 8.19 Hz, 2 H, Ar-H), 8.22 (t, ³J = 8.2 Hz, 6 H, Ar-H), 8.42

3

(d, J = 8.8 Hz, 2 H, Ar-H), 8.67 (d, ³J = 8.2 Hz, 2 H, Ar-H), 8.77

5-(3-Methoxyphenyl)-10,20-diphenyl-15-(trimethylsilanylethynyl)por-

phyrin (66): Following general procedure F, using 19 (120 mg,

0.185 mmol), PdCl₂(PPh₃)₂(19.5 mg, 0.028 mmol), CuI (8.8 mg,

0.047 mmol), and ethynyl(trimethyl)silane (0.26 mL, 1.85 mmol).

The solution was stirred for 12 h at 50 °C. All solvents removed

and residue purified via column chromatography (silica, CH₂Cl₂/

hexane, 1:2, v/v) to yield a purple product as the main fraction;

3

(d, J = 4.7 Hz, 2 H, H_β), 8.86 (d, J = 4.7 Hz, 2 H, H_β), 8.91 (m,

4 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 83.6, 121.9,

126.7, 127.8, 128.5, 130.0, 130.6, 131.8, 134.4, 134.7, 135.1 ppm.

UV/Vis (CH₂Cl₂): λ_max(logε) = 419 (4.91), 515 (3.69), 551 (3.48),

592 (3.36), 645 nm (3.31). HRMS (MS ES⁺) m/z calcd. for

[C₄₆H₃₀N₅O₂] [M + H⁺]: 684.2400; found 684.2391.

5,15-Bis(3,5-di-tert-butylphenyl)-10-phenyl-20-(trimethylsilanyleth- yield 59.2 mg (0.089 mmol, 48 %); m.p. Ͼ 300 °C. ¹H NMR

ynyl)porphyrin (62): Produced from 15 (180 mg, 0.214 mmol),

PdCl₂(PPh₃)₂(10.0 mg, 0.143 mmol), CuI (4.0 mg, 5.3 mmol), and

ethynyl(trimethyl)silane (0.20 g, 2.04 mmol) according to general

procedure F. All solvents were removed and the brown residue puri-

(600 MHz, CDCl₃): δ = –2.39 (s, 2 H, NH), 0.65 [s, 9 H, Si(CH₃)

3

₃] 4.00 (s, 3 H, OCH₃), 7.34–7.36 (dd, J_H,H= 2.5 Hz, 1 H, Ar-H),

3

7.64–7.67 (t, J_H,H= 15.8 Hz, 2 H, Ar-H), 7.81 (m, 8 H, Ar-H),

3

8.23–8.24 (d, J_H,H= 6.5 Hz, 4 H, Ph-H), 8.79–8.80 (d, J_H,H

=

Eur. J. Org. Chem. 2011, 5817–5844

www.eurjoc.org

5831

M. O. Senge et al.

FULL PAPER

4.6 Hz, 2 H, H_β), 8.85–8.86 (d, ³J_H,H= 4.6 Hz, 2 H, H_β), 8.92–8.93 H, H_β), 9.08–9.09 (d, ³J_H,H= 4.5 Hz, 2 H, H_β), 9.76–9.77 (d, ³J_H,H

3

(d, J_H,H= 4.4 Hz, 2 H, H_β), 9.69–9.70 (d, J_H,H= 4.6 Hz, 2 H,

H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 13.9, 22.5, 29.6, 31.4,

55.3, 98.9, 101.8, 106.9, 113.5, 120.2, 120.9, 121.5, 126.6, 127.4,

= 4.6 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 21.0,

29.5, 30.2, 31.6, 34.9, 83.1, 86.0, 97.8, 120.8, 122.7, 123.2, 125.4,

126.4, 127.4, 128.1, 129.6, 130.6, 132.0, 133.3, 134.1, 135.6, 141.3,

127.7, 130.9, 134.4, 141.5, 143.1, 157.8 ppm. UV/Vis (THF): λ_max142.5, 148.6, 149.7, 150.2, 150.8, 151.4, 152.5 ppm. UV/Vis (THF):

(logε) = 427 (5.27), 525 (3.90), 563 (4.02), 602 (3.43), 654 nm (3.35).

HRMS (ESI) m/z calcd. for C₄₄H₃₇N₄OSi [M + H]⁺665.2737;

found 665.2759.

λ_max(logε) = 429 (5.31), 566 (3.91), 608 nm (3.76). HRMS (ESI)

m/z calcd. for C₅₆H₅₉N₄[M]⁺848.3796; found 848.3836.

5,15-Bis(3,5-di-tert-butylphenyl)-10-ethynyl-20-hexylporphyrin (73):

5-(4-Nitrophenyl)-15-trimethylsilanylethynyl-10,20-diphenylpor- Produced from 64 (23 mg, 0.025 mmol) in CH₂Cl₂(10 mL) and

phyrin (67): Following general procedure G, 25 (60 mg, TBAF in THF (1 m, 0.1 mL, 0.1 mmol) following general pro-

0.090 mmol), ethynyltrimethylsilane (0.14 mL, 0.1 mmol), CuI cedure H. After stirring for 20 min, the solution was filtered

(4 mg, 0.023 mmol), and Pd(PPh₃)₂Cl₂(6 mg, 0.009 mmol) gave through a plug of silica and washed with CH₂Cl₂(50 mL). All sol-

40 mg (0.058 mmol, 65%) of a purple solid after recrystallization

from CH₂Cl₂/MeOH; m.p. Ͼ300 °C; R_f= 0.2 (CH₂Cl₂/n-hexane =

2:1, v/v). ¹H NMR (400 MHz, CDCl₃, TMS): δ = –2.44 (s, 2 H,

NH), 0.63 [s, 9 H, Si(CH₃)₃], 7.81 (m, 6 H, Ar-H), 8.21 (d, ³J =

vents were removed to yield a purple solid; yyield 20 mg

1

(0.023 mmol, 93%); m.p. Ͼ 300 °C. H NMR (400 MHz, CDCl₃,

3

TMS): δ = –2.33 (s, 2 H, NH), 0.94–0.98 (t, J_H,H= 14.5 Hz, 3 H,

CH₃), 1.42 (m, 4 H, CH₂), 1.58 (s, 36 H, tBuH), 1.86 (m, 2 H,

CH₂), 2.57 (m, 2 H, CH₂), 4.17 (s, 1 H, CϵCH), 5.00 (m, 2 H,

CH₂), 7.84 (s, 4 H, Ar-H), 8.07 (m, 2 H, Ar-H), 8.91 (m, 4 H, H_β),

3

7.8 Hz, 4 H, Ar-H), 8.38 (d, J = 7.8 Hz, 2 H, Ar-H), 8.65 (d, J

3

= 8.8 Hz, 2 H, Ar-H), 8.69 (d, J = 4.9 Hz, 2 H, H_β), 8.83 (d, J =

4.7 Hz, 2 H, H_β), 8.93 (d, ³J = 4.9 Hz, 2 H, H_β), 9.70 (d, ³J =

4.9 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 0.2, 99.5,

102.1, 117.9, 121.0, 121.4, 126.4, 127.6, 134.1, 134.5, 140.9, 147.3,

148.5 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 429 (4.87), 528 (3.55),

566 (3.70), 605 (3.30), 661 nm (3.40). HRMS (MS ES⁺) m/z calcd.

for [C₄₃H₃₄N₅O₂Si] [M + H⁺]: 680.2482; found 680.2493.

3

9.45–9.46 (d, J_H,H= 4.7 Hz, 2 H, H_β), 9.63–9.64 (d, J_H,H

=

4.7 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 13.9,

22.6, 30.2, 31.7, 34.9, 35.7, 38.7, 83.3, 35.6, 96.2, 120.9, 121.7,

122.7, 129.5, 129.6, 140.8, 148.7 ppm. UV/Vis (THF): λ_max(logε)

= 428 (5.48), 525 (4.10), 562 (4.14), 603 (3.69), 661 nm (3.79).

HRMS (ESI) m/z calcd. for C₅₆H₆₇N₄[M + H]⁺795.5366; found

795.5378.

5-Ethynyl-10,15,20-triphenylporphyrin (69): Produced from 59

(43 mg, 0.08 mmol) following general procedure H. Purple crystals

were isolated (27 mg, 0.05 mmol, 61%); m.p. Ͼ 300 °C. H NMR

10-Ethynyl-20-(3-methoxyphenyl)-5,15-diphenylporphyrin (75): Pro-

duced from 66 (25 mg, 0.038 mmol) following general procedure H

to yield a purple solid (20 mg, 0.034 mmol, 90%); m.p. Ͼ 300 °C.

1

(400 MHz, CDCl₃, TMS): δ = –2.49 (s, 2 H, NH), 4.19 (s, 1 H,

CH), 7.76 (m, 9 H, Ph-H), 8.25–8.14 (m, 6 H, Ph-H), 8.78 (d, ³J_H,H¹H NMR (400 MHz, CDCl₃, TMS): δ = –2.45 (s, 2 H, NH), 4.00

3

= 5.7 Hz, 4 H, H_β), 8.91 (d, J_H,H= 4.8 Hz, 2 H, H_β), 9.69 (d,

³J_H,H= 4.7 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ =

53.2, 83.8, 85.4, 97.3, 120.9, 122.1, 126.5, 126.6, 127.7, 130.8, 134.2,

134.3, 141.5, 141.8 ppm. UV/Vis (CH₂Cl₂): λ_max(log ε) = 425

(5.56), 525 (4.28), 560 (4.17), 599 (3.73), 655 nm (3.71). HRMS

(ESI) m/z calcd. for C₄₀H₂₇N₄[M + H]⁺563.2236; found 563.2231.

(s, 3 H, OCH₃), 4.22 (s, 1 H, CϵCH), 7.35–7.37 (m, 3 H, Ar-H),

7.64–7.68 (m, 2 H, Ar-H), 7.81 (m, 6 H, Ph-H), 8.22–8.24 (d, ³J_H,H

= 6.8 Hz, 2 H, Ph-H), 8.79–8.80 (d, ³J_H,H= 4.7 Hz, 2 H, H_β), 8.85–

3

8.86 (d, J_H,H= 4.3 Hz, 2 H, H_β), 8.93–8.94 (d, J_H,H= 4.0 Hz, 2

H, H_β), 9.71–9.72 (d, J_H,H= 4.1 Hz, 2 H, H_β) ppm. ¹³C NMR

3

(150 MHz, CDCl₃): δ = 25.5, 29.6, 30.2, 34.1, 55.6, 37.8, 83.8, 85.4,

97.4, 112.5, 120.3, 120.9, 121.7, 125.4, 126.7, 127.4, 127.7, 131.1,

134.4, 135.7, 141.5, 143.1, 157.8 ppm. UV/Vis (THF): λ_max(logε)

= 423 (5.58), 523 (4.19), 558 (4.13), 601 (3.66), 662 nm (3.38).

HRMS (ESI) m/z calcd. for C₄₁H₂₉N₄O [M + H]⁺593.2327; found

593.2341.

5,15-Bis(3,5-di-tert-butylphenyl)-10-ethynyl-20-phenylporphyrin

(71): Produced from 62 (130 mg, 0.151 mmol) in CH₂Cl₂(80 mL)

and TBAF in THF (1 m, 0.5 mL, 0.5 mmol) following general pro-

cedure H. After 20 min, the solution was filtered through a plug of

silica and washed with CH₂Cl₂(50 mL). All solvents were removed

to yield a purple solid; yyield 112 mg (0.142 mmol, 94%); m.p. Ͼ

300 °C. ¹H NMR (600 MHz, CDCl₃): δ = –2.37 (s, 2 H, NH), 1.51

(s, 36 H, tBuH), 4.19 (s, 1 H, CϵC-H), 7.70–7.80 (m, 3 H, Ph-H),

7.81–7.83 (m, 2 H, Ph-H), 8.05–8.09 (m, 4 H, Ph-H), 8.18–8.21 (m,

5-Ethynyl-15-(4-nitrophenyl)-10,20-diphenylporphyrin (76): Follow-

ing general procedure H, TBAF in THF (0.1 mL, 1 m) was added

to a solution 67 (40 mg, 0.059 mmol) in CH₂Cl₂(20 mL). The reac-

tion mixture was stirred for 20 min and the crude product was puri-

fied by recrystallization from CH₂Cl₂/MeOH to give 33 mg

(0.054 mmol, 92 %) of a purple solid; m.p. Ͼ300 °C; R_f= 0.4

(CH₂Cl₂/n-hexane = 1:1, v/v). ¹H NMR (400 MHz, CDCl₃, TMS):

δ = –2.49 (s, 2 H, NH), 4.24 (s, 1 H, CϵCH), 7.82 (m, 6 H, Ar-

H), 8.22 (d, ³J = 6.4 Hz, 4 H, Ar-H), 8.39 (d, ³J = 8.8 Hz, 2 H,

3

2 H, Ph-H), 8.79 (d, J_H,H= 4.7 Hz, 2 H, H_β), 8.82 (d, J_H,H

=

3

4.7 Hz, 2 H, H_β), 8.97 (d, J_H,H= 4.7 Hz, 2 H, H_β), 9.70 (d, J_H,H

= 4.7 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 31.6,

34.9, 83.6, 85.7, 121.1, 121.8, 122.3, 126.5, 127.7, 129.8, 134.2,

140.5, 142.0, 148.8 ppm. UV/Vis (CH₂Cl₂): λ_max(log ε) = 427

(5.79), 527 (4.39), 562 (4.36), 602 (3.93), 659 nm (4.00). HRMS

(ESI) m/z calcd. for C₅₆H₅₉N₄[M + H]⁺787.4727; found 787.4740.

3

Ar-H), 8.65 (d, ³J = 8.8 Hz, 2 H, Ar-H), 8.70 (d, J = 4.7 Hz, 2 H,

H_β), 8.85 (d, ³J = 4.7 Hz, 2 H, H_β), 8.96 (d, ³J = 4.9 Hz, 2 H, H_β),

9.73 (d, ³J = 4.9 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃):

δ = 84.3, 98.3, 107.8, 112.9, 118.4, 121.3, 121.7, 126.4, 126.7, 127.8,

130.3, 134.8, 141.2, 147.7, 148.8 ppm. UV/Vis (CH₂Cl₂): λ_max(logε)

= 426 (4.85), 524 (3.56), 561 (3.54), 599 (3.23), 673 nm (2.83).

HRMS: m/z calcd. for [C₄₀H₂₃N₅O₂]: 605.1852; found 605.1994.

[5,15-Bis(3,5-di-tert-butylphenyl)-10-ethynyl-20-phenylporphyrinato-

]zinc(II) (72): Following general procedure H, 72 was produced

from 63 (100 mg, 0.117 mmol) in CH₂Cl₂(30 mL) and TBAF in

THF (1 m, 0.5 mL, 0.500 mmol). After stirring for 20 min the solu-

tion was filtered through a plug of silica and washed with CH₂Cl₂.

All solvents were removed in vacuo to yield a purple solid; yyield

86 mg (0.109 mmol, 94%); m.p. Ͼ 300 °C. ¹H NMR (600 MHz,

5-Ethynyl-10,20-diphenylporphyrin (77): Following general pro-

cedure H, TBAF in THF (0.2 mL, 0.0002 mmol, 1 m) was added

CDCl₃, TMS): δ = 1.59 (s, 36 H, tBuH), 4.09 (s, 1 H, CϵC-H), to a solution of 60 (75 mg, 0.133 mmol) in CH₂Cl₂(20 mL). The

3

7.78 (m, 3 H, Ph-H), 7.86 (m, 2 H, Ar-H), 8.12–8.13 (d, J_H,H

=

reaction mixture was stirred for 20 min. The solvent was removed

under reduced pressure and the residue dissolved in CH₂Cl₂and

filtered through a short silica gel column. Recrystallization from

1.7 Hz, 4 H, Ar-H), 8.22–8.23 (d, ³J_H,H= 6.5 Hz, 2 H, Ph-H), 8.93–

8.94 (d, J_H,H= 4.5 Hz, 2 H, H_β), 8.97–8.98 (d, J_H,H= 4.6 Hz, 2

3

5832

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Eur. J. Org. Chem. 2011, 5817–5844

Unsymmetrical meso-Substituted Porphyrin Dimers and Arrays

CH₂Cl₂/MeOH gave purple crystals (60 mg, 0.123 mmol, 92%);

m.p. Ͼ 300 °C; R_f= 0.5 (CH₂Cl₂/n-hexane = 1:1, v/v). H NMR

Table 1. Bromination of 81.

1

Product

Equivalents of NBS

3

(400 MHz, CDCl₃, TMS): δ = –2.7 (s, 2 H, NH), 4.23 (s, 1 H,

1.5

1

0.8

3

CϵCH), 7.83 (m, 6 H, Ar-H), 8.26 (m, 4 H, Ar-H), 8.98 (d, J =

4.1 Hz, 2 H, H_β), 9.01 (d, ³J = 4.7 Hz, 2 H, H_β), 9.33 (d, ³J =

4.7 Hz, 2 H, H_β), 9.79 (d, ³J = 4.7 Hz, 2 H, H_β), 10.27 (s, 1 H,

H_meso) ppm. ¹³C NMR (125 MHz, CDCl₃, TMS): δ = 83.7, 85.7,

97.8, 106.6, 120.3, 126.7, 127.7, 130.5, 131.0, 131.4, 131.6, 134.4,

141.1 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 420 (4.76), 517 (3.38),

552 (3.28), 592 (3.28), 649 nm (2.98). HRMS (MS ES⁺) m/z calcd.

for [C₃₄H₂₃N₄] [M + H⁺]: 487.1910; found 487.1923.

82

83/84

85

86

81

93

–

1.5

5.3

31

15.5

–

4

41

13.8

10

4.1

60

21.4

5

5,10-Dibromo-15-(1-ethylpropyl)porphyrin (83): The compound was

obtained from the synthesis of 82 by purification of a small amount

of the mixed fraction 83/84 by chromatography; m.p. Ͼ 300 °C; R_f

5,10,15-Triphenyl-20-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-

porphyrin (79): Produced from 17 (63 mg, 0.102 mmol) with

Pd(PPh₃)₄(23 mg, 0.020 mmol) and pinacolborane (1.530 mmol,

0.20 mL) following general procedure C. After purification using

column chromatography, 79 was obtained as a purple solid (37 mg,

0.056 mmol, 54%); m.p. Ͼ 300 °C. ¹H NMR (400 MHz, CDCl₃,

TMS): δ = –2.80 (br. s, 2 H, NH), 1.84 (s, 12 H CH₃), 7.76 (m, 9

1

= 0.57 (CH₂Cl₂/n-hexane = 1:1, v/v). H NMR (600 MHz, CDCl₃,

TMS): δ = –3.04 (s, 1 H, NH), –2.77 (s, 1 H, NH), 1.00 [t, J =

7.3 Hz, 6 H, CH(CH₂CH₃)₂], 2.83 [m, 2 H, CH(CH₂CH₃)₂], 2.95

[m, 2 H, CH(CH₂CH₃)₂], 4.99 [m, 1 H, CH(CH₂CH₃)₂], 9.16 (d, J

= 4.4 Hz, 1 H, H_β), 9.28 (br. s, 1 H, H_β), 9.49 (d, J = 4.4 Hz, 1 H,

H_β), 9.52 (d, J = 4.4 Hz, 1 H, H_β), 9.64 (br. s, 2 H, H_β), 9.69 (d, J

3

H, m, p-Ph–H), 8.20 (m, 6 H, o-Ph–H), 8.81 (d, J_H,H= 4.6 Hz, 2

3

H, H_β), 8.84 (d, J_H,H= 4.6 Hz, 2 H, H_β), 8.97 (d, J_H,H= 4.6 Hz, = 4.0 Hz, 1 H, H_β), 9.82 (br. s, 1 H, H_β), 9.93 (br. s, 1 H, H_meso

)

2 H, H_β), 9.86 (d, J_H,H= 4.6 Hz, 2 H, H_β) ppm. ¹³C NMR ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 13.9, 29.5, 31.7, 34.5, 50.1,

3

(150 MHz, CDCl₃): δ = 28.9, 84.8, 119.6, 121.3, 126.2, 127.2, 127.3,

134.1, 134.1, 141.6, 141.9 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 417

(5.40), 513 (4.03), 547 (3.76), 587 (3.49), 641 nm (3.40). HRMS

97.3, 101.2, 103.6, 105.3, 107.1, 129.3, 131.8, 132.1, 133.1, 133.7,

145.3, 146.7 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 415 (5.07), 515

(3.84), 548 (3.50), 593 (3.36), 652 nm (3.21). HRMS (MS ES⁺) m/z

(ESI) m/z calcd. for C₄₄H₃₇N₄O₂B [M]⁺665.3088; found 665.3081. calcd. for [C₂₅H₂₃N₄Br₂] [M + H⁺]: 537.0289; found 537.0289.

5-Bromo-15-(1-ethylpropyl)porphyrin (85): Obtained from the syn-

thesis of 82 as purple crystals (30 mg, 0.065 mmol, 31%); m.p.

Ͼ300 °C; R_f= 0.45 (CH₂Cl₂/n-hexane = 1:1, v/v). ¹H NMR

(600 MHz, CDCl₃, TMS): δ = –2.90 (s, 1 H, NH), –2.69 (s, 1 H,

NH), 1.00 [t, J = 7.0 Hz, 6 H, CH(CH₂CH₃)₂], 2.89 [m, 2 H,

CH(CH₂CH₃)₂], 3.01 [m, 2 H, CH(CH₂CH₃)₂], 5.08 [m, 1 H,

CH(CH₂CH₃)₂], 9.38 (d, J = 4.4 Hz, 2 H, H_β), 9.42 (m, 2 H, H_β),

9.69 (d, J = 4.4 Hz, 2 H, H_β), 9.72 (br. s, 1 H, H_β), 9.77 (br. s, 1

H, H_β), 10.18 (s, 2 H, H_meso) ppm. ¹³C NMR (150 MHz, CDCl₃):

δ = 13.9, 34.5, 49.9, 99.9, 105.0, 105.4, 123.8, 128.7, 129.1, 130.8,

131.1, 132.0, 132.5 ppm. UV/Vis (CH₂Cl₂): λ_max(log ε) = 406

(4.69), 505 (3.32), 537 (2.71), 580 (3.54), 640 nm (2.13). HRMS

(MS ES⁺) m/z calcd. for [C₂₅H₂₄N₄Br] [M + H⁺]: 459.1184; found

459.1193.

5,10,15-Trihexyl-20-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-

porphyrin (80): Produced from 20 (64 mg, 0.100 mmol) with

Pd(PPh₃)₄(23 mg, 0.020 mmol) and pinacolborane (1.500 mmol,

0.13 mL), following general procedure C. The flask was stirred for

7 h to avoid degradation of products. After purification, 80 was

obtained as a purple solid (35 mg, 0.051 mmol, 51 %); m.p. Ͼ

1

300 °C. H NMR (400 MHz, CDCl₃): δ = –2.65 (s, 2 H, NH) 0.95

(m, 12 H, 5-CH₂), 1.42 (m, 6 H, 5-CH₂), 1.53 (m, 6 H, 4-CH₂),

3

1.85–1.75 (m, 6 H, 3-CH₂), 1.87 (s, 12 H, CH₃), 2.54 (d, J_H,H

=

3

7.0 Hz, 6 H, 2-CH₂), 4.95 (s, 6 H, 1-CH₂), 9.46 (d, J_H,H= 4.3 Hz,

2 H, H_β), 9.58–9.48 (m, 4 H, H_β), 9.84 (d, J_H–H= 4.1 Hz, 2 H,

3

H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 14.0, 22.6, 25.1, 30.1,

30.2, 31.8, 35.4, 35.7, 38.5, 38.7, 84.9, 118.7, 121.2, 128.1 ppm. UV/

Vis: λ_max(log ε) = 421(5.46), 517 (4.11), 553 (3.76), 595 (3.57),

652 nm (3.47). HRMS (ESI) m/z calcd. for C₄₄H₆₂N₄O₂B

[M + H]⁺689.4966; found 689.4977.

5-Bromo-10-(1-ethylpropyl)porphyrin (86): Obtained from the syn-

thesis of 82 (15 mg, 0.032 mmol, 16 %) as purple crystals; m.p.

Ͼ300 °C; R_f= 0.37 (CH₂Cl₂/n-hexane = 1:1, v/v). ¹H NMR

(400 MHz, CDCl₃, TMS): δ = –3.22 (br. s, 2 H, NH), 0.98 [t, J =

7.3 Hz, 6 H, CH(CH₂CH₃)₂], 2.86 [m, 2 H, CH(CH₂CH₃)₂], 3.00

[m, 2 H, CH(CH₂CH₃)₂], 5.13 [m, 1 H, CH(CH₂CH₃)₂], 9.33 (m,

2 H, H_β), 9.39 (m, 2 H, H_β), 9.76 (m, 2 H, H_β), 9.82 (d, J = 4.4 Hz,

1 H, H_β), 9.90 (br. s, 1 H, H_β), 10.02 (s, 1 H, H_meso), 10.18 (s, 1 H,

H_meso) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 14.1, 34.9, 50.5,

103.1, 103.9, 104.5, 104.7, 124.8, 129.1, 129.6, 130.8, 131.7, 133.4,

145.3, 148.5 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 409 (4.72), 505

(3.65), 539 (3.32), 581 (3.42), 656 nm (3.36). HRMS: m/z calcd. for

(MS ES⁺) [C₂₅H₂₄N₄Br] [M + H⁺]: 459.1184; found 459.1180.

5,10,15-Tribromo-20-(1-ethylpropyl)porphyrin (82): Following gene-

ral procedure A, 81 (80 mg, 0.21 mmol), NBS (56.13 mg,

0.315 mmol), pyridine (1.0 mL), and acetone (10 mL) in CHCl₃

(70 mL) were used. The products were separated on column

chromatography using silica gel (n-hexane/ethyl acetate = 10:1,

v/v) followed by a second column eluting with the same solvents.

The first fraction was 82 (2 mg, 0.0032 mmol, 1.5%) as purple crys-

tals, the second fraction 84 and 83 (6 mg, 0.011 mmol, 5%) as pur-

ple crystals, the third fraction 85 (30 mg, 0.065 mmol, 31%) as pur-

ple crystals, and the fourth fraction gave 86 (15 mg, 0.032 mmol,

15.5%) as purple crystals. For optimization of the yields of individ-

ual compounds see Table 1; m.p. Ͼ 300 °C; R_f= 0.8 (n-hexane/

ethyl acetate = 10:1, v/v). H NMR (400 MHz, CDCl₃): δ = –2.69 general procedure D, 85 (20 mg, 0.0435 mmol), (3-hydroxyphenyl)-

5-(1-Ethylpropyl)-15-(3-hydroxyphenyl)porphyrin (87): Following

1

(s, 1 H, NH), –2.53 (s, 1 H, NH), 0.97 [t, J = 7.0 Hz, 6 H,

boronic acid (75 mg, 0.543 mmol), Pd(PPh₃)₄(5 mg, 0.004 mmol),

CH(CH₂CH₃)₂], 2.78 [m, 2 H, CH(CH₂CH₃)₂], 2.90 [m, 2 H, and K₃PO₄(231 mg, 1.087 mmol) in THF (50 mL) were used. Puri-

CH(CH₂CH₃)₂], 4.96 [m, 1 H, CH(CH₂CH₃)₂], 9.56 (d, J = 4.7 Hz, fication by column chromatography on silica gel (CH₂Cl₂/n-hexane

2 H, H_β), 9.60 (m, 2 H, H_β), 9.65 (d, J = 4.7 Hz, 2 H, H_β), 9.7 (m, = 4:1, v/v) followed by a second column using CH₂Cl₂/n-hexane =

2 H, H_β) ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 422 (5.05), 526

(3.69), 561 (3.65), 609 (3.27), 667 nm (3.40). HRMS (MS ES⁺) m/z

calcd. for [C₂₅H₂₂N₄Br₃] [M + H⁺]: 614.9395; found 614.9385. See

Table 1 for the optimum conditions for each compound.

2:1 (v/v) and recrystallization from CH₂Cl₂/CH₃OH gave purple

crystals (5 mg, 0.010 mmol, 24%); m.p. Ͼ300 °C; R_f= 0.5 (CH₂Cl₂/

1

n-hexane = 4:1, v/v). H NMR (400 MHz, CDCl₃): δ = –2.77 (s, 2

H, NH), 0.99 [m, 6 H, CH(CH₂CH₃)₂], 2.88 [m, 2 H, CH(CH₂-

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5833

M. O. Senge et al.

FULL PAPER

CH₃)₂], 3.04 [m, 2 H, CH(CH₂CH₃)₂], 5.5 (s, 1 H, OH), 5.13 [m, 1

(4.75), 505 (3.67), 537 (3.37), 580 (3.28), 634 nm (3.15). HRMS

H, -CH(CH₂CH₃)₂], 7.67 (t, J = 7.6 Hz, 1 H, Ar-H), 7.74 (s, 2 H, (MS ES⁺) m/z calcd. for [C₃₀H₃₃N₄Si] [M + H⁺]: 477.2467; found

Ar-H), 7.84 (m, 1 H, Ar-H), 9.26 (s, 2 H, H_β), 9.39 (d, J = 4.7 Hz,

2 H, H_β), 9.48 (m, 2 H, H_β), 9.80 (m, 2 H, H_β), 10.29 (s, 2 H,

H_meso) ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 406 (4.64), 503 (3.28),

545 (2.90), 575 (2.91), 629 nm (2.60). HRMS (MS ES⁺) m/z calcd.

for [C₃₁H₂₉N₄O] [M + H⁺]: 473.2341; found 473.2336.

477.2475.

5-(1-Ethylpropyl)-10,15,20-tris(trimethylsilanylethynyl)porphyrin

(91): Following general procedure G, 82 (150 mg, 0.243 mmol), eth-

ynyltrimethylsilane (1.1 mL, 0.8 mmol), CuI (12 mg, 0.06 mmol),

and Pd(PPh₃)₂Cl₂(17 mg, 0.024 mmol) in triethylamine (15 mL)

and THF (5 mL) were used. Purification by column chromatog-

raphy on silica gel using CH₂Cl₂/n-hexane (1:2, v/v) followed by

recrystallization from CH₂Cl₂/CH₃OH gave purple crystals (80 mg,

5-(1-Ethylpropyl)-15-(3-nitrophenyl)porphyrin (88): Following gene-

ral procedure D, 85 (20 mg, 0.044 mmol), (3-nitrophenyl)boronic

acid (91 mg, 0.543 mmol), Pd(PPh₃)₄(5 mg, 0.004 mmol), and

K₃PO₄(231 mg, 1.087 mmol) in THF (50 mL) were used. Purifica-

tion by column chromatography on silica gel (CH₂Cl₂/n-hexane =

1:2, v/v) followed by recrystallization from CH₂Cl₂/CH₃OH gave

purple cyrstals (8 mg, 0.0159 mmol, 38%); m.p. Ͼ300 °C; R_f= 0.5

(CH₂Cl₂/n-hexane = 1:1, v/v). ¹H NMR (400 MHz, CDCl₃, TMS):

δ = –2.61 (s, 1 H, NH), –2.45 (s, 1 H, NH), 0.99 [t, J = 7.0 Hz, 6

H, CH(CH₂CH₃)₂], 2.87 [m, 2 H, CH(CH₂CH₃)₂], 3.00 [m, 2 H,

CH(CH₂CH₃)₂], 4.22 (s, 1 H, CH), 5.08 [m, 1 H, CH(CH₂CH₃)₂],

8.01 (d, J = 7.5 Hz, 1 H, Ar-H), 8.60 (d, J = 7.2 Hz, 2 H, Ar-H),

8.71 (d, J = 7.5 Hz, 1 H, Ar-H), 8.97 (d, J = 3.8 Hz, 2 H, H_β), 9.16

(s, 1 H, H_β), 9.44 (d, J = 4.5 Hz, 2 H, H_β), 9.49 (m, 2 H, H_β), 9.79

(br. s, 1 H, H_β), 9.84 (br. s, 1 H, H_β), 10.33 (s, 2 H, H_meso) ppm.

¹³C NMR (150 MHz, CDCl₃): δ = 13.9, 29.8, 49.9, 104.9, 105.3,

114.3, 123.9, 128.7, 129.1, 131.8, 132.3, 140.0, 142.9, 146.6,

147.2 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 407 (4.74), 505 (3.70),

538 (3.39), 577 (3.30), 637 nm (3.00). HRMS (MS ES⁺) m/z calcd.

for [C₃₁H₂₈N₅O₂] [M + H⁺]: 502.2243; found 502.2237.

0.012 mmol, 49%); m.p. Ͼ300 °C; R_f= 0.84 (n-hexane/CH₂Cl₂

=

4:1, v/v). ¹H NMR (400 MHz, CDCl₃, TMS): δ = –1.82 (s, 1 H,

NH), –1.74 (s, 1 H, NH), 0.64 [s, 27 H, Si(CH₃)₃], 0.95 [t, J =

7.3 Hz, 6 H, CH(CH₂CH₃)₂], 2.77 [m, 2 H, CH(CH₂CH₃)₂], 2.90

[m, 2 H, CH(CH₂CH₃)₂], 4.95 [m, 1 H, CH(CH₂CH₃)₂], 9.53 (m,

3 H, H_β), 9.57 (br. s, 1 H, H_β), 9.62 (d, J = 4.8 Hz, 2 H, H_β), 9.67

(m, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 14.0, 34.5,

50.3, 99.9, 102.4, 102.5, 105.7, 106.8, 127.6, 129.2, 130.3,

131.6 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 445 (4.77), 556 (3.12),

595 (3.90), 636 (2.52), 696 nm (3.30). HRMS (MS ES⁺) m/z calcd.

for [C₄₀H₄₉N₄Si₃] [M + H⁺]: 669.3295; found 669.3265.

5-Ethenyl-15-(1-ethylpropyl)porphyrin (92): Following general pro-

cedure H, 90 (35 mg, 0.073 mmol) and a 1 m solution TBAF

(0.2 mL, 0.0002 mmol) in THF and CH₂Cl₂(20 mL) were used.

Recrystallization gave purple crystals (23 mg, 0.056 mmol, 77%);

m.p. Ͼ300 °C; R_f= 0.6 (CH₂Cl₂/n-hexane = 1:1, v/v). ¹H NMR

(400 MHz, CDCl₃): δ = –2.61 (s, 1 H, NH), –2.45 (s, 1 H, NH), 0.99

[t, J = 7.0 Hz, 6 H, CH(CH₂CH₃)₂], 2.87 [m, 2 H, CH(CH₂CH₃)₂],

3.00 [m, 2 H, CH(CH₂CH₃)₂], 4.22 (s, 1 H CH), 5.08 [m, 1 H,

CH(CH₂CH₃)₂], 9.41 (d, J = 4.7 Hz, 4 H, H_β), 9.72 (d, J = 4.7 Hz,

4 H, H_β), 10.22 (s, 2 H, H_meso) ppm. ¹³C NMR (150 MHz, CDCl₃):

δ = 13.7, 29.2, 34.2, 49.7, 83.2, 84.2, 105.5, 125.0, 128.4, 128.8,

129.1, 129.3, 131.1, 132.1 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 411

(4.70), 512 (3.43), 548 (3.44), 584 (3.11), 640 nm (3.00). HRMS

(MS ES⁺) m/z calcd. for [C₂₇H₂₅N₄] [M + H⁺]: 405.2068; found

405.2069.

5-(1-Ethylpropyl)-15-(4-methoxycarbonylphenyl)porphyrin (89): Fol-

lowing general procedure D, 85 (20 mg, 0.044 mmol), (4-methoxyc-

arbonylphenyl)boronic acid (86 mg, 0.435 mmol), Pd(PPh₃)₄(5 mg,

0.004 mmol), and K₃PO₄(185 mg, 0.870 mmol) in THF (50 mL)

were used. Purification by column chromatography on silica gel (n-

hexane/CH₂Cl₂= 1:1, v/v) followed by recrystallization from

CH₂Cl₂/CH₃OH afforded purple crystals (5 mg, 0.001 mmol, 67%);

m.p. Ͼ300 °C; R_f= 0.5 (CH₂Cl₂/n-hexane = 1:2, v/v). ¹H NMR

(400 MHz, CDCl₃, TMS): δ = –2.81 (s, 1 H, NH), –2.73 (s, 1 H,

NH), 1.00 [t, J = 7.0 Hz, 6 H, CH(CH₂CH₃)₂], 2.89 [m, 2 H,

CH(CH₂CH₃)₂], 3.02 [m, 2 H, CH(CH₂CH₃)₂], 4.16 (s, 6 H,

OCH₃), 5.13 [m, 1 H, CH(CH₂CH₃)₂], 8.37 (d, J = 8.2 Hz, 2 H,

Ar-H), 8.51 (d, J = 8.2 Hz, 2 H, Ar-H), 9.03 (d, J = 4.1 Hz, 2 H,

H_β), 9.42 (d, J = 4.7 Hz, 2 H, H_β), 9.49 (m, 2 H, H_β), 9.78 (m, 1

H, H_β), 9.83 (d, 1 H, H_β), 10.32 (s, 2 H, H_meso) ppm. ¹³C NMR

(150 MHz, CDCl₃): δ = 13.9, 29.0, 34.5, 52.2, 53.2, 104.7, 116.5,

128.1, 129.2, 131.9, 134.7, 145.9, 146.7 ppm. UV/Vis (CH₂Cl₂):

λ_max(logε) = 406 (5.14), 504 (4.01), 537 (3.71), 576 (3.41), 633 nm

(3.21). HRMS (MS ES⁺) m/z calcd. for [C₃₃H₃₁N₄O₂] [M + H⁺]:

515.2447; found 515.2447.

5-(1-Ethylpropyl)-10,15,20-triethynylporphyrin (93): Following ge-

neral procedure H, 91 (70 mg, 0.104 mmol) and a 1 m TBAF solu-

tion in THF (0.3 mL, 0.0003 mmol) dissolved in CH₂Cl₂(20 mL)

were used. Recrystallization from CH₂Cl₂/MeOH gave purple crys-

tals (30 mg, 0.070 mmol, 63%); m.p. Ͼ300 °C; R_f= 0.66 (CH₂Cl₂/

n-hexane = 1:1, v/v). ¹H NMR (400 MHz, CDCl₃, TMS): δ = –2.04

(s, 1 H, NH), –1.94 (s, 1 H, NH), 0.98 [t, J = 7.0 Hz, 6 H,

CH(CH₂CH₃)₂], 2.80 [m, 2 H, CH(CH₂CH₃)₂], 2.92 [m, 2 H,

CH(CH₂CH₃)₂], 4.18 (s, 2 H, CH), 4.23 (s, 1 H, CH), 4.99 [m, 1

H, CH(CH₂CH₃)₂], 9.55–9.65 (m, 8 H, H_β) ppm. ¹³C NMR

(150 MHz, CDCl₃): δ = 14.1, 22.7, 29.7, 30.0, 31.9, 34.6, 50.4, 84.6,

127.9, 129.5, 129.8, 130.8, 131.8, 146.2 ppm. UV/Vis (CH₂Cl₂):

λ_max(logε) = 436 (4.70), 541 (4.70), 581 (3.80), 621 (3.32), 684 nm

(3.50). HRMS (MS ES⁺) m/z calcd. for [C₃₁H₂₅N₄] [M + H⁺]:

453.2094; found 453.2079.

5-(1-Ethylpropyl)-15-trimethylsilanylethynylporphyrin (90): Follow-

ing procedure G, 85 (46 mg, 0.1 mmol), ethynyltrimethylsilane

(0.152 mL, 0.11 mmol), CuI (5 mg, 0.025 mmol), and Pd(PPh₃)₂Cl₂

(7 mg, 0.01 mmol) were added to triethylamine (15 mL) and THF

(5 mL). Purification by column chromatography on silica gel

5-(10Ј,15Ј,20Ј-Triphenylporphyrin-5Ј-yl)-10,15,20-tris(3-methoxy-

(CH₂Cl₂/n-hexane = 1:2, v/v) followed by recrystallization from phenyl)porphyrin (94): Produced from 79 (5 mg, 0.0075 mmol), 20

CH₂Cl₂/CH₃OH afford purple crystals (38 mg, 0.008 mmol, 79%); (5 mg, 0.007 mmol), Cs₂CO₃(6 mg, 0.03 mmol), and Pd(PPh₃)₄

1

m.p. Ͼ300 °C; R_f= 0.48 (n-hexane/CH₂Cl₂= 4:1, v/v). H NMR (1 mg, 0.0008 mmol) following general procedure E. After purifica-

(400 MHz, CDCl₃): δ = –2.48 (s, 2 H, NH), 0.66 [s, 9 H, Si- tion, a dark purple solid was isolated (3 mg, 0.003 mmol, 29%);

(CH₃)₃], 0.98 [t, J = 7.01 Hz, 6 H, CH(CH₂CH₃)₂], 2.83 [m, 2 H, m.p. Ͼ 300 °C. ¹H NMR (400 MHz, CDCl₃, TMS): δ = –2.24–2.28

CH(CH₂CH₃)₂], 2.99 [m, 2 H, CH(CH₂CH₃)₂], 5.05 [m, 1 H, (m, 4 H, NH), 3.94 (s, 3 H, OCH₃), 4.07 (s, 3 H, OCH₃), 7.57 (m,

CH(CH₂CH₃)₂], 9.39 (d, J = 4.4 Hz, 4 H, H_β), 9.72 (d, J = 4.8 Hz,

3 H, Ph-H), 7.71 (m, 8 H, Ph-H), 7.83 (m, 8 H, Ph-H), 7.89–7.83

3

4 H, H_β), 10.20 (s, 2 H, H_meso) ppm. ¹³C NMR (150 MHz, CDCl₃): (m, 3 H, Ph-H), 8.09–8.10 (d, J_H,H= 4.8 Hz, 4 H, H_β), 8.24–8.26

3

δ = 14.1, 34.6, 50.1, 97.1, 101.6, 105.6, 106.0, 125.2, 128.8, 129.7,

129.8, 131.5, 131.7, 132.2 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 406

(d, J_H,H= 6.8 Hz, 4 H, Ph-H), 8.31–8.34 (d, J_H,H= 5.5 Hz, 4 H,

3

Ph-H), 8.61–8.62 (d, J_H,H= 4.0 Hz, 2 H, H_β), 8.65–8.66 (d, J_H,H

5834

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Eur. J. Org. Chem. 2011, 5817–5844

Unsymmetrical meso-Substituted Porphyrin Dimers and Arrays

= 4.8 Hz, 2 H, H_β), 8.97 (m, 8 H, H_β) ppm. ¹³C NMR (150 MHz,

CDCl₃): δ = 14.1, 22.7, 29.4, 31.9, 41.0, 126.6, 126.7, 127.7, 128.8,

134.4 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 406 (5.20), 503 (3.94),

533 (3.53), 574 nm (3.48). HRMS (MALDI-TOF) m/z calcd. for

C₇₉H₅₆N₈O₃[M]⁺1165.4554; found 1165.4497.

(4.97), 452 (4.10), 525 (4.34), 564 (3.96), 601 (3.87), 661 nm (3.79).

HRMS (MALDI) m/z calcd. for C₇₉H₈₁N₈O₃[M + H]⁺1189.6432;

found 1189.6471.

5-Butyl-10,20-bis(4-methoxyphenyl)-15-(10Ј,15Ј,20Ј-triphenylpor-

phyrin-5Ј-ylethynyl)porphyrin (98): Produced from 69 (10 mg,

0.018 mmol), 23 (12 mg, 0.018 mmol), AsPh₃(4 mg, 0.013 mmol),

5-Butyl-10,15-bis(4-methoxyphenyl)-20-(10Ј,15Ј,20Ј-triphenylpor-

phyrin-5Ј-yl)porphyrin (95):^[48]Produced from 79 (10 mg, and Pd₂(dba)₃(5 mg, 0.001 mmol) following procedure J. After pu-

0.015 mmol), 23 (10 mg, 0.015 mmol), Cs₂CO₃(10 mg, 0.05 mmol), rification dark green crystals were isolated (5 mg, 0.004 mmol,

and Pd(PPh₃)₄(2 mg, 0.002 mmol) following general procedure E 29%); m.p. Ͼ 300 °C. ¹H NMR (400 MHz, CDCl₃, TMS): δ =

1

3

to give a green solid (9 mg, 0.008 mmol, 48%); m.p. Ͼ 300 °C. H

–2.02 (s, 2 H, NH), –1.93 (s, 2 H, NH), 1.15 (t, J_H,H= 7.4 Hz, 6

NMR (400 MHz, CDCl₃, TMS): δ = –2.23 (s, 2 H, NH) –2.15 (s,

H, CH₃), 1.88–1.81 (m, 2 H, CH₂), 2.57–2.51 (m, 2 H, CH₂), 4.14

(s, 6 H, OCH₃), 4.98 (m, 2 H, CH₂), 7.35 (m, 4 H, Ar-H), 7.80 (m,

2 H, NH), 1.18–1.22 (t, ³J_H,H= 14.7 Hz, 3 H, CH₃), 1.87 (m, 2 H,

CH₂), 2.60 (m, 2 H, CH₂), 4.05 (s, 6 H, OCH₃), 5.13 (m, 2 H, CH₂), 9 H, Ph-H), 8.17 (m, 4 H, Ar-H), 8.22 (m, 2 H, Ph-H), 8.29 (m, 4

3

7.23–7.35 (d, J_H,H= 8.8 Hz, 4 H, Ar-H), 7.71 (m, 6 H, Ph-H), H, Ph-H), 8.80 (m, 4 H, H_β), 8.90–8.91 (d, J_H,H= 4.7 Hz, 2 H,

3

7.84 (m, 2 H, Ph-H), 8.04–8.05 (d, J_H,H= 4.9 Hz, 2 H, Ph-H), H_β), 9.07 (m, 4 H, H_β), 9.44 (d, J_H,H= 4.8 Hz, 2 H, H_β), 10.24

8.12 (d, J_H,H= 8.6 Hz, 6 H, Ar-H), 8.23 (m, 4 H, H_β), 8.31–8.33

(d, J_H,H= 5.4 Hz, 2 H, Ph-H), 8.60 (m, 4 H, H_β), 8.91 (m, 4 H,

H_β), 9.02–9.03 (d, J_H,H= 4.9 Hz, 2 H, H_β), 9.61–9.62 (d, J_H–H

4.9 Hz, 2 H, H_β) ppm. UV/Vis: λ_max(logε) = 430 (4.90), 522 (3.58),

558 (3.60), 605 nm (3.65). HRMS (MALDI-TOF) m/z calcd. for

C₇₆H₅₉N₈O₂[M + H]⁺1115.4761; found 1115.4783.

3

(d, J_H,H= 4.7 Hz, 2 H, H_β), 10.32 (d, J_H,H= 4.7 Hz, 2 H, H_β)

ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 14.0, 14.1, 22.5, 23.5, 29.2,

29.6, 29.9, 31.8, 55.5, 112.2, 120.7, 127.8, 128.2, 128.7, 128.8, 130.3,

134.3, 134.4, 134.7, 135.4, 141.7 ppm. UV/Vis (CH₂Cl₂): λ_max(logε)

= 415 (4.73), 470 (4.72), 518 (3.89), 620 (3.93), 717 nm (4.00).

HRMS (MALDI-TOF) m/z calcd. for C_{7 8}H₅₈N₈O₂[M]⁺

1138.4683; found 1138.4803.

3

=

10,15,20-Tris(4-methoxyphenyl)-5-(10Ј,15Ј,20Ј-trihexylporphyrin-5Ј-

yl)porphyrin (96): Produced from 80 (10 mg, 0.015 mmol), 22

(12 mg, 0.02 mmol), Cs₂CO₃(4 mg, 0.02 mmol), and Pd(PPh₃)₄

(3 mg, 0.003 mmol) following general procedure E to give a green

solid (6 mg, 0.005 mmol, 37 %); m.p. Ͼ 300 °C. ¹H NMR

10,15,20-Tris(3-methoxyphenyl)-5-(5Ј,10Ј,20Ј-triphenylporphyrin-

5Ј-ylethynyl)porphyrin (99): Produced from 69 (10 mg,

0.018 mmol), 21 (13 mg, 0.018 mmol), AsPh₃(5 mg, 0.020 mmol),

and Pd(PPh₃)₄(2 mg, 0.001 mmol) following procedure J. After pu-

(400 MHz, CDCl₃, TMS): δ = –2.14 (s, 2 H, NH), –2.05 (s, 2 H, rification dark green crystals were isolated (3 mg, 0.002 mmol,

NH), 0.91–0.82 (m, 12 H, CH₂), 1.38 (m, 6 H CH₂), 1.45 (m, 6 H, 29%); m.p. Ͼ 300 °C. ¹H NMR (400 MHz, CDCl₃, TMS): δ =

CH₂), 1.76 (m, 4 H, CH₂), 1.92 (m, 2 H, CH₂), 2.54 (m, 4 H, CH₂), –2.03 (s, 2 H, NH) –2.01 (s, 2 H, NH), 3.98 (s, 3 H, OCH₃), 4.01

3

2.63 (m, 2 H, CH₂), 4.04 (s, 6 H, OCH₃), 4.18 (s, 3 H, OCH₃), 4.94 (s, 6 H, OCH₃), 7.10 (d, J_H,H= 15.9 Hz, 4 H, Ar-H), 7.63 (m, 6

3

(m, 4 H, CH₂), 5.11–5.15 (t, ³J_H,H= 15.6 Hz, 2 H, CH₂), 7.24–7.25 H, Ph-H), 7.75 (d, J_H,H= 15.9 Hz, 4 H, Ar-H), 7.91–7.87 (m, 3

3

(d, J_H,H= 8.3 Hz, 4 H, Ph-H), 7.38–7.39 (d, J_H,H= 8.3 Hz, 2 H,

H, Ph-H), 8.24–8.20 (m, 3 H, Ph-H), 8.32–8.27 (m, 4 H, Ph-H),

8.83–8.81 (m, 3 H, H_β), 8.87–8.85 (m, 3 H, H_β), 8.95–8.90 (m, 3

H, H_β), 9.11–9.08 (m, 2 H, H_β), 9.15–9.12 (m, 2 H, H_β), 9.35–9.32

(m, 1 H, H_β), 10.37–10.32 (m, 4 H, H_β) ppm. ¹³C NMR (150 MHz,

3

Ph-H), 8.05–8.06 (d, J_H,H= 4.9 Hz, 2 H, H_β), 8.08–8.09 (d, J_H,H

= 4.4 Hz, 2 H, H_β), 8.16–8.18 (d, ³J_H,H= 8.8 Hz, 4 H, Ph-H) 8.25–

3

8.26 (d, J_H,H= 8.3 Hz, 2 H, Ph-H) 8.63–8.64 (d, J_H,H= 4.9 Hz,

3

2 H, H_β), 8.96–8.97 (d, J_H,H= 4.9 Hz, 2 H, H_β), 9.00–9.01 (d, CDCl₃): δ = 14.0, 22.5, 22.6, 29.2, 29.7, 29.9, 31.8, 55.5, 125.3,

³J_H,H= 4.9 Hz, 2 H, H_β), (m, 4 H, H_β), 9.13–9.14 (d, J_H,H

=

126.7, 127.5, 127.9, 128.2, 128.8, 130.3, 134.3, 134.4, 136.7,

3

4.4 Hz, 2 H, H_β), 9.58–9.60 (d, ³J_H,H= 4.0 Hz, 2 H, H_β), 9.66–9.67 143.2 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 412 (4.91), 473 (4.88),

3

(d, J_H,H= 4.9 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃):

δ = 13.9, 14.0, 22.5, 22.7, 29.5, 29.6, 30.1, 30.2, 31.7, 31.9, 38.5,

55.3, 112.0, 112.1, 135.3 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 410

(5.67), 450 (5.01), 507 (4.48), 567 (3.95), 599 (3.87), 666 nm (3.49).

HRMS (MALDI-TOF) m/z calcd. for C₇₉H₈₁N₈O₃[M + H]⁺

1189.6432; found 1189.6428.

517 (4.01), 620 (4.09), 713 nm (4.19). HRMS (MALDI-TOF) m/z

calcd. for C₈₁H₅₆N₈O₃[M]⁺1188.4475; found 1188.4490.

10,20-Bis(3,5-di-tert-butylphenyl)-15-phenyl-5-[5Ј,10Ј,20Ј-tris(4-

methoxyphenyl)porphyrin-5Ј-ylethynyl]porphyrin (100): Following

procedure J, 71 (20.0 mg, 0.025 mmol), 22 (18 mg, 0.025 mmol),

AsPh₃(10 mg, 0.033 mmol), and Pd₂(dba)₃(2 mg, 0.003 mmol)

were dried in vacuo and dissolved in degassed NEt₃(1 mL) and

THF (4 mL). The solution was stirred for 14 h at 65 °C. All sol-

vents were removed and the residue purified by column chromatog-

10,15,20-Tris(3-methoxyphenyl)-5-(10Ј,15Ј,20Ј-trihexylporphyrin-5Ј-

yl)porphyrin (97): Produced from 80 (10 mg, 0.015 mmol), 21

(8 mg, 0.01 mmol), Cs₂CO₃(4 mg, 0.02 mmol), and Pd(PPh₃)₄

(2 mg, 0.002 mmol) following general procedure E to give a purple

raphy (silica, CH₂Cl₂/hexane, 1:4 to 2:1, v/v) to yield a red-green

1

solid; yield = 8 mg (0.007 mmol, 51%); m.p. Ͼ 300 °C. H NMR solid; yyield 23 mg (0.016 mmol, 64%); m.p. Ͼ 300 °C. H NMR

(400 MHz, CDCl₃, TMS): δ = –2.16 (s, 2 H, NH) –2.07 (s, 2 H, (400 MHz, CDCl₃, TMS): δ = –1.92 (s, 2 H, NH), –1.89 (s, 2 H,

NH), 0.86 (m, 12 H, CH₃), 1.00 (m, 6 H CH₂), 1.36–1.30 (m, 8 H, NH), 1.59 (s, 36 H, tBu–H), 4.11 (s, 3 H, CH₃), 4.14 (s, 6 H, CH₃),

CH₂), 1.77 (m, 4 H, CH₂), 1.92–1.86 (m, 2 H, CH₂) 2.50 (m, 4 H, 7.31 (d, J_H,H= 8.2 Hz, 2 H, Ph-H), 7.31 (d, J_H,H= 8.8 Hz, 4 H,

CH₂), 2.62 (m, 2 H, CH₂), 4.01 (s, 6 H, OCH₃), 4.14 (s, 3 H, Ph-H), 7.74–7.80 (m, 3 H, Ph-H), 7.85–7.89 (m, 4 H, Ph-H), 8.15

3

OCH₃), 4.94–4.85 (m, 4 H, CH₂), 5.14–5.06 (m, 2 H, CH₂), 7.21

(d, ³J_H,H= 8.2 Hz, 2 H, Ph-H), 8.17–8.21 (m, 4 H, Ph-H), 8.23 (d,

³J_H,H= 8.8 Hz, 4 H, Ph-H), 8.84–8.93 (m, 8 H, H_β), 9.17 (d, ³J_H,H

3

(d, J_H,H= 8.6 Hz, 4 H, Ph-H), 8.03 (d, J_H,H= 4.7 Hz, 2 H, H_β),

3

8.07 (d, J_H,H= 4.7 Hz, 2 H, H_β), 8.14 (d, J_H,H= 8.6 Hz, 4 H,

= 4.6 Hz, 2 H, H_β) 9.20 (d, J_H,H= 4.7 Hz, 2 H, H_β) 10.40 (m, 4

Ph-H), 8.22 (d, J_H,H= 8.3 Hz, 2 H, H_β), 8.61 (d, J_H,H= 4.7 Hz, H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 35.2, 55.6, 55.6,

3

2 H, H_β), 8.96 (dd, J_H,H= 13.2, 4.7 Hz, 4 H, H_β), 9.11 (d, J_H,H99.9, 100.2, 100.3, 100.3, 112.3, 112.4, 121.2, 121.3, 121.8, 122.9,

3

= 4.9 Hz, 2 H, H_β), 9.56 (d, J_H,H= 4.7 Hz, 2 H, H_β), 9.63 (d,

³J_H,H= 4.8 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ =

13.9, 14.0, 22.8, 29.6, 30.1, 30.3, 38.6, 55.7, 110.0, 112.0, 113.4,

134.1, 135.3, 137.1 ppm. UV/Vis (CH₂Cl₂): λ_max(log ε) = 413

126.7, 129.8, 134.3, 134.3, 135.5, 135.6, 140.8, 149.0, 159.6 ppm.

UV/Vis (CH₂Cl₂): λ_max(logε) = 409 (4.77), 475 (4.95), 522 (4.05),

623 (4.22), 719 nm (4.34). HRMS (ESI) m/z calcd. for C₉₇H₈₈N₈O₃

[M + H]⁺1413.7086; found 1413.7058.

Eur. J. Org. Chem. 2011, 5817–5844

www.eurjoc.org

5835

M. O. Senge et al.

10,20-Bis(3,5-di-tert-butylphenyl)-15-phenyl-5-[(5Ј,10Ј,20Ј-tri- 8.24 (m, 2 H, Ph-H), 8.79 (d, J_H,H= 4.7 Hz, 2 H, Ph-H), 8.84 (d,

FULL PAPER

3

hexylporphyrin-5Ј-yl)ethynyl]porphyrin (101): Following procedure

J, 71 (21 mg, 0.027 mmol), 20 (17 mg, 0.027 mmol), AsPh₃(25 mg,

³J_H,H= 4.7 Hz, 2 H, Ph-H), 8.92 (d, ³J_H,H= 4.7 Hz, 2 H, H_β), 9.06

3

(d, J_H,H= 4.7 Hz, 2 H, H_β), 9.11 (d, J_H,H= 4.7 Hz, 2 H, H_β),

0.082 mmol), and Pd₂(dba)₃(16 mg, 0.028 mmol) were dried in 9.44 (s, 2 H, H_β), 10.27 (s, 4 H, H_β), 10.33 (s, 4 H, H_β) ppm. ¹³C

vacuo and dissolved in degassed NEt₃(1 mL) and THF (4 mL).

The solution was stirred for 4 h at 65 °C and then for 15 h at room

temperature. All solvents were removed and the residue purified by

column chromatography (silica, CH₂Cl₂/hexane, 1:4 to 1:1, v/v) to

yield a red-green solid; yyield 16 mg (0.012 mmol, 45%); m.p. Ͼ

300 °C. ¹H NMR (600 MHz, CDCl₃, TMS): δ = –1.93 (s, 2 H,

NH), –1.89 (s, 2 H, NH), 0.94–1.00 (m, 9 H, CH₃), 1.38–1.49 (m,

6 H, CH₂), 1.51–1.60 (m, 6 H, CH₂), 1.59 (s, 36 H, tBu–H), 1.81–

1.91 (m, 6 H, CH₂), 2.51–2.61 (m, 6 H, CH₂), 4.91–4.98 (m, 6 H,

NMR (150 MHz, CDCl₃): δ = 14.0, 22.6, 25.5, 29.3, 29.4, 29.6,

30.2, 30.3, 34.9, 121.1, 122.2, 122.7, 124.7, 125.4, 126.5, 129.5,

129.6, 134.2, 135.5, 140.7, 140.9 ppm. UV/Vis (CH₂Cl₂): λ_max(logε)

= 408 (4.94), 474 (5.13), 521 (4.24), 622 (4.38), 721 nm (4.50).

HRMS (ESI) m/z calcd. for C₁₁₀H₁₁₄N₈[M]⁺1546.9166; found

1546.9181.

5,5Ј-(1,2-Ethyndiyl)bis[10,20-bis(3,5-di-tert-butylphenyl)-15-phenyl-

porphyrin] (104): Following procedure J, 71 (18 mg, 0.023 mmol),

15 (19 mg, 0.023 mmol), AsPh₃(10 mg, 0.033 mmol), and Pd₂-

(dba)₃(1 mg, 0.002 mmol) were dried in vacuo and dissolved in

degassed NEt₃(1 mL) and THF (4 mL). The solution was stirred

for 6 h at 65 °C. All solvents were removed and the residue purified

by column chromatography (silica, CH₂Cl₂/hexane, 1:4 to 2:1, v/v)

to yield a red-green solid; yyield 15 mg (0.010 mmol, 43%); m.p. Ͼ

300 °C. ¹H NMR (600 MHz, CDCl₃, TMS): δ = –1.93 (s, 4 H,

NH), 1.58 (s, 72 H, tBu–H), 7.72–7.81 (m, 6 H, Ph-H), 7.83–7.87

(m, 4 H, Ph-H), 8.13–8.18 (m, 8 H, Ph-H), 8.21–8.26 (m, 4 H, Ph-

H), 8.79 (s, 4 H, H_β), 8.86 (s, 4 H, H_β), 9.14 (s, 4 H, H_β), 10.36 (s,

4 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 35.0, 53.3, 99.8,

100.2, 121.1, 121.6, 122.7, 126.6, 127.6, 129.7, 134.2, 140.7, 142.0,

148.8 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 413 (4.59), 474 (4.72),

523 (3.87), 622 (3.99), 718 nm (4.09). HRMS (ESI) m/z calcd. for

CH₂), 7.72–7.80 (m, 3 H, Ph-H), 7.83–7.86 (m, 2 H, Ph-H), 8.13–

3

8.16 (m, 4 H, Ph-H), 8.21–8.25 (m, 2 H, Ph-H), 8.81 (d, J_H,H

=

3

4.7 Hz, 2 H, H_β), 8.88 (d, J_H,H= 4.7 Hz, 2 H, H_β), 9.17 (d, J_H,H

= 4.7 Hz, 2 H, H_β), 9.45 (d, ³J_H,H= 4.7 Hz, 2 H, H_β) 9.49 (d, ³J_H,H

3

= 4.7 Hz, 2 H, H_β), 9.61 (d, J_H,H= 4.7 Hz, 2 H, H_β), 10.32 (d,

³J_H,H= 4.7 Hz, 2 H, H_β), 10.37 (d, J_H,H= 4.7 Hz, 2 H, H_β) ppm.

3

¹³C NMR (150 MHz, CDCl₃): δ = 14.1, 14.2, 22.7, 22.8, 29.7, 29.8,

30.3, 30.4, 31.8, 31.9, 35.1, 35.4, 36.0, 98.4, 99.4, 100.3, 100.7,

120.8, 121.3, 121.6, 121.8, 122.8, 126.7, 127.8, 128.4, 128.9, 129.9,

133.7, 134.3, 140.9, 142.2, 149.0 ppm. UV/Vis (CH₂Cl₂): λ_max(logε)

= 410 (4.61), 473 (4.82), 522 (3.85), 623 (4.04), 723 nm (4.17).

HRMS (ESI) m/z calcd. for C₉₄H₁₀₆N₈[M + H]⁺1347.8606; found

1347.8619.

C

₁₁₀H₁₁₄N₈[M + H]⁺1547.9292; found 1547.9245.

10,20-Bis(3,5-di-tert-butylphenyl)-15-phenyl-[5-(5Ј,10Ј,20Ј-tri-

phenylporphyrin-5Ј-yl)ethynyl]porphyrin (102): Following procedure

J, 71 (20 mg, 0.025 mmol), 17 (16 mg, 0.025 mmol), AsPh₃(10 mg,

0.033 mmol), and Pd₂(dba)₃(2 mg, 0.002 mmol) were dried in

vacuo and dissolved in degassed NEt₃(1 mL) and THF (4 mL).

The solution was stirred for 4 h at 65 °C and then for 15 h at room

temperature. All solvents were removed and the residue purified by

column chromatography (silica, CH₂Cl₂/hexane, 1:3 to 1:1, v/v) to

yield a red-green solid; yyield 15 mg (0.012 mmol, 45%); m.p. Ͼ

300 °C. ¹H NMR (600 MHz, CDCl₃, TMS): δ = –2.00 (s, 2 H,

NH), –1.94 (s, 2 H, NH), 1.58 (s, 36 H, tBu–H), 7.74–7.85 (m, 12

H, Ph-H), 7.83–7.86 (m, 2 H, Ph-H), 8.15–8.18 (m, 4 H, Ph-H),

8.21–8.26 (m, 4 H, Ph-H), 8.28–8.34 (m, 4 H, Ph-H), 8.80–8.90 (m,

8 H, H_β), 9.11 (d, ³J_H,H= 4.7 Hz, 2 H, H_β), 9.15 (d, ³J_H,H= 4.7 Hz,

[5-{10Ј,20Ј-Bis(3,5-di-tert-butylphenyl)-15Ј-phenylporphyrin-5Ј-

yl}ethynyl-10,15,20-triphenylporphyrinato]zinc(II) (105): Following

procedure J, 71 (32 mg, 0.040 mmol), 52 (27 mg, 0.040 mmol),

AsPh₃(20.2 mg, 0.066 mmol), and Pd₂(dba)₃(9.0 mg, 0.010 mmol)

were dried in vacuo and dissolved in degassed NEt₃(1 mL) and

THF (4 mL). The solution was stirred for 4 h at 65 °C and then for

15 h at room temperature. All solvents were removed and the resi-

due purified by column chromatography (silica, CH₂Cl₂/hexane, 1:4

to 1:1, v/v) to yield a red-green solid; yyield 30 mg (0.022 mmol,

54%); m.p. Ͼ 300 °C. ¹H NMR (600 MHz, CDCl₃, TMS): δ =

–1.93 (s, 2 H, NH), 1.58 (s, 36 H, tBu–H), 7.70–7.83 (m, 12 H, Ph-

H), 7.85–7.87 (m, 4 H, Ph-H), 8.15–8.18 (m, 4 H, Ph-H), 8.22–8.25

(m, 2 H, Ph-H), 8.29–8.32 (m, 4 H, Ph-H), 8.80 (d, ³J_H,H= 4.7 Hz,

2 H, H_β), 8.87 (d, ³J_H,H= 4.7 Hz, 2 H, H_β), 8.88 (d, ³J_H,H= 4.7 Hz,

2 H, H_β), 8.92 (d, ³J_H,H= 4.7 Hz, 2 H, H_β), 9.13 (d, ³J_H,H= 4.7 Hz,

3

2 H, H_β), 10.36 (d, J_H,H= 4.7 Hz, 2 H, H_β), 10.37 (d, J_H,H

=

4.7 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 35.1,

53.4, 99.7, 100.1, 100.4, 100.7, 121.3, 121.5, 121.9, 122.0, 123.0,

126.7, 126.8, 126.9, 127.8, 127.9, 129.8, 134.3, 134.4, 134.6, 140.8,

141.8, 142.0, 142.2, 149.0 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 406

(4.80), 474 (4.99), 521 (4.31), 624 (4.37), 719 nm (4.42). HRMS

(ESI) m/z calcd. for C₉₄H₈₂N₈[M + H]⁺1323.6749; found

1323.6741.

3

2 H, H_β), 9.19 (d, J_H,H= 4.7 Hz, 2 H, H_β), 10.33 (d, J_H,H

=

4.7 Hz, 2 H, H_β) 10.43 (d, ³J_H,H= 4.7 Hz, 2 H, H_β) ppm. ¹³C NMR

(150 MHz, CDCl₃): δ = 31.7, 35.0, 99.7, 100.0, 100.3, 101.8, 121.1,

121.6, 121.9, 122.3, 122.7, 126.4, 126.6, 127.6, 129.7, 130.8, 131.9,

132.2, 133.2, 134.1, 134.2, 134.3, 140.7, 142.4, 148.8, 149.9, 150.1,

150.5, 152.8 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 406 (4.86), 473

(4.99), 521 (4.31), 624 (4.37), 716 nm (4.42). HRMS (ESI) m/z

calcd. for C₉₄H₈₀N₈Zn [M + H]⁺1385.5930; found 1385.5876.

5-[5Ј,15Ј-Bis(3,5-di-tert-butylphenyl)-10Ј-phenylporphyrin-5Ј-yl]-

ethynyl-10,20-bis(3,5-di-tert-butylphenyl)-15-hexylporphyrin (103):

Following procedure J, 73 (30 mg, 0.039 mmol), 15 (33 mg,

0.039 mmol), AsPh₃(10 mg, 0.033 mmol), and Pd₂(dba)₃(4 mg, Dizinc(II) Complex of 5-[10Ј,20Ј-Bis(3,5-di-tert-butylphenyl)-15Ј-

0.004 mmol) were dried in vacuo and dissolved in degassed NEt₃

(1 mL) and THF (4 mL). The solution was stirred for 6 h at 65 °C.

All solvents were removed and the residue purified by column

chromatography (silica, CH₂Cl₂/hexane, 1:4 to 2:1, v/v) to yield a

red-green solid; yyield 20 mg (0.013 mmol, 34%); m.p. Ͼ 300 °C.

phenylporphyrin-5Ј-yl)ethynyl]-10,15,20-triphenylporphyrin (106):

Following procedure J, 72 (28 mg, 0.033 mmol), 52 (22 mg,

0.033 mmol), AsPh₃(15 mg, 0.049 mmol), and Pd₂(dba)₃(5 mg,

0.005 mmol) were dried in vacuo and dissolved in degassed NEt₃

(1 mL) and THF (4 mL). The solution was stirred at 65 °C for 16 h.

¹H NMR (600 MHz, CDCl₃, TMS): δ = –1.95 (s, 2 H, NH), –1.88 All solvents were removed and the residue purified by column

(s, 2 H, NH), 1.57 (s, 36 H, tBu–H), 1.59 (s, 36 H, tBu–H), 0.94– chromatography (silica, CH₂Cl₂/hexane, 1:4 to 1:1, v/v) to yield a

0.98 (m, 3 H, CH₃), 1.41–1.47 (m, 2 H, CH₂), 1.64–1.70 (m, 2 H,

CH₂), 1.83–1.90 (m, 2 H, CH₂), 2.55–2.60 (m, 2 H, CH₂), 4.94– ¹H NMR (600 MHz, CDCl₃, TMS): δ = 1.59 (s, 36 H, tBu-H),

5.02 (m, 2 H, CH₂), 7.72–7.80 (m, 3 H, Ph-H), 7.83–7-87 (m, 2 H, 7.70–7.83 (m, 14 H, Ph-H), 8.15–8.22 (m, 8 H, Ph-H), 8.29–8.32

Ph-H), 7.83–7.86 (m, 2 H, Ph-H), 8.12–8.16 (m, 4 H, Ph-H), 8.20– (m, 4 H, Ph-H), 8.89 (s, 2 H, H_β), 8.92 (s, 4 H, H_β), 8.97 (s, 2 H,

red-brown solid; yyield 25 mg (0.017 mmol, 52%); m.p. Ͼ 300 °C.

5836

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Eur. J. Org. Chem. 2011, 5817–5844

Unsymmetrical meso-Substituted Porphyrin Dimers and Arrays

H_β), 9.18 (s, 2 H, H_β), 9.23 (s, 2 H, H_β), 10.43 (s, 4 H, H_β) ppm.

HRMS (ESI) m/z calcd. for C₇₈H₅₈N₈[M + H]⁺1107.4904; found

¹³C NMR (150 MHz, CDCl₃): δ = 31.8, 35.1, 121.0, 122.4, 122.8, 1107.4863.

123.9, 126.6, 126.7, 127.7, 129.7, 130.7, 131.0, 132.0, 132.3, 132.3,

1,2-Bis(5,10,15-triphenylporphyrin-20-yl)ethyne (110): Produced

133.3, 133.6, 134.2, 134.3, 134.4, 141.5, 142.5, 148.8, 150.0, 150.1,

150.3, 150.3, 150.6, 150.9, 152.8, 152.9 ppm. UV/Vis (CH₂Cl₂):

λ_max(log ε) = 413 (4.63), 480 (4.92), 559 (4.22), 690 nm (4.35).

HRMS (ESI) m/z calcd. for C₉₄H₇₈N₈Zn₂[M + H]⁺1447.4935;

found 1447.5011.

from 69 (80 mg, 0.142 mmol), 10 (76 mg, 0.142 mmol), AsPh₃

(48 mg, 0.156 mmol), and Pd₂(dba)₃(13 mg, 0.014 mmol) using ge-

neral procedure J. The solvent was removed in vacuo and the resi-

due filtered through a plug of silica using CH₂Cl₂/Et₃N as eluent

(99:1, v/v) giving a green fraction. After removal of the solvent and

recrystallization from CH₂Cl₂/MeOH a dark powder was obtained

(75 mg, 0.068 mmol, 48%); m.p. Ͼ 300 °C. ¹H NMR (400 MHz,

CDCl₃, TMS): δ = –1.96 (s, 2 H, NH) 7.81 (m, 18 H, Ph-H), 8.23

(m, 6 H, Ph-H), 8.32 (m, 8 H, Ph-H), 8.84 (m, 8 H, H_β), 9.11–9.13

(d, 4 H, H_β), 10.36–10.38 (d, 4 H, H_β) ppm. ¹³C NMR (150 MHz,

[D₈]THF): δ = 29.5, 53.3, 126.6, 126.9, 128.0, 134.2, 134.5

141.6 ppm. UV/Vis (THF): λ_max(logε) = 407 (5.04), 472 (5.24),

519 (5.29), 619 (4.44), 712 nm (4.53). HRMS (ESI) m/z calcd. for

C₇₈H₄₆N₈[M + H]⁺1099.4255; found 1099.4237.

Dizinc(II) Complex of 10,20-Bis(3,5-di-tert-butylphenyl)-15-phenyl-

5-[(5Ј,10Ј,20Ј-trihexylporphyrin-5Ј-yl)ethynyl]porphyrin (107): Di-

mer 101 (11 mg, 0.008 mmol) was dissolved in CHCl₃(10 mL) and

heated to reflux for 10 min. Zinc(II) acetate (100 mg, 0.406 mmol)

was dissolved in methanol (2 mL) and both solutions were com-

bined. The mixture was heated to reflux for 30 min. All solvents

were removed in vacuo, the residue dissolved in CH₂Cl₂(5 mL) and

filtered through a plug of silica. All solvents were removed to yield

a red/brown solid; yyield 8 mg (0.006 mmol, 68%); m.p. Ͼ 300 °C.

¹H NMR (600 MHz, [D₈]THF, TMS): δ = 0.94–0.99 (m, 9 H,

CH₃), 1.42–1.48 (m, 6 H, CH₂), 1.54–1.60 (m, 6 H, CH₂), 1.61 (s,

36 H, tBu–H), 1.86–1.94 (m, 6 H, CH₂), 2.54–2.65 (m, 6 H, CH₂),

5.03–5.12 (m, 6 H, CH₂), 7.74–7.78 (m, 3 H, Ph-H), 7.93–7.95 (m,

Zinc(II) Complex of 1,2-Bis(5,10,15-triphenylporphyrin-20-yl)ethyne

(111): Produced from 74 (70 mg, 0.112 mmol), 52 (67 mg,

0.112 mmol), AsPh₃(38 mg, 0.123 mmol), and Pd₂(dba)₃(10 mg,

0.011 mmol) using general procedure J. The solvent was removed

in vacuo and the residue filtered through a plug of silica using

CH₂Cl₂/Et₃N as eluent (99:1, v/v), to yield a green fraction.

Recrystallization from CH₂Cl₂/MeOH gave a dark powder (75 mg,

0.068 mmol, 47%); m.p. Ͼ 300 °C. ¹H NMR (400 MHz, CDCl₃,

TMS): δ = 7.83 (m, 20 H, Ph-H), 8.26 (m, 4 H, Ph-H), 8.33 (m, 6

H, Ph-H), 8.95–8.96 (d, 8 H, H_β), 9.23–9.24 (d, 4 H, H_β), 10.51–

10.52 (d, 4 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 98.8,

99.2, 120.3, 120.7, 124.6, 124.6, 125.7, 128.5, 129.6, 129.8, 130.8,

132.6, 132.8, 141.6, 141.7, 148.1, 148.4, 148.8, 151.1 ppm. UV/Vis

(CH₂Cl₂): λ_max(logε) = 412 (5.18), 479 (5.44), 548 (4.36), 685 nm

(4.74). HRMS (ESI) m/z calcd. for C₇₈H₄₆N₈Zn₂[M]⁺1222.2428;

found 1222.2468.

3

2 H, Ph-H), 8.19–8.25 (m, 6 H, Ph-H), 8.78 (d, J_H,H= 4.7 Hz, 2

3

H, H_β), 8.84 (d, J_H,H= 4.7 Hz, 2 H, H_β), 9.16 (d, J_H,H= 4.7 Hz,

2 H, H_β), 9.57 (d, ³J_H,H= 4.7 Hz, 2 H, H_β) 9.59 (d, ³J_H,H= 4.7 Hz,

2 H, H_β), 9.77 (d, J_H,H= 4.7 Hz, 2 H, H_β), 10.43 (d, J_H,H

3

=

4.7 Hz, 2 H, H_β), 10.49 (d, J_H,H= 4.7 Hz, 2 H, H_β) ppm. ¹³C

NMR (150 MHz, [D₈]THF, TMS): δ = 14.5, 23.7, 30.7, 31.2, 32.1,

33.0, 35.8, 40.0, 121.7, 122.0, 122.8, 124.0, 125.9, 127.2, 129.4,

130.6, 130.7, 131.3, 132.5, 133.6, 135.2, 138.2, 143.5, 149.5, 150.2,

150.5, 15.1, 151.2, 151.6, 153.2, 153.7 ppm. UV/Vis (CH₂Cl₂): λ_max

(logε) = 432 (4.45), 479 (4.78), 557 (4.21), 696 nm (4.38). HRMS

(ESI) m/z calcd. for C₉₄H₁₀₂N₈Zn₂[M + H]⁺1471.6903; found

1471.6889.

3

15-(3-Methoxyphenyl)-10,20-diphenyl-5-[(5Ј,10Ј,20Ј-triphenylpor-

phyrin-5Ј-yl)ethynyl]porphyrin (108):^[48]Obtained from 75 (25 mg,

0.042 mmol), 10 (26 mg, 0.042 mmol), AsPh₃(27 mg, 0.089 mmol),

and Pd₂(dba)₃(3.8 mg, 0.004 mmol) using general procedure J to

yield a dark green solid following column chromatography CH₂Cl₂/

Hex (1:3, v/v); yield (18 mg, 0.016 mmol, 38%); m.p. Ͼ 300 °C. ¹H

NMR (400 MHz, CDCl₃, TMS): δ = –2.09 (s, 2 H, NH), –1.99 (s,

2 H, NH), 4.02 (s, 3 H, OCH₃), 7.54 (m, 4 H, Ar-H), 7.84 (m, 16

H, Ar-H), 8.27 (m, 8 H, Ph-H), 8.82 (m, 8 H, H_β), 9.03–9.04 (d,

2-(5-Butyl-10,20-diphenylporphyrin-5-yl)-1-[15Ј-(4-nitrophenyl)-

10Ј,20Ј-diphenylporphyrin-5Ј-yl]ethyne (112): Following general

procedure J, 76 (21 mg, 0.033 mmol), 26 (20 mg, 0.033 mmol),

AsPh₃(20 mg, 0.066 mmol), and Pd₂(dba)₃(8 mg, 0.008 mmol)

were added to a mixture of THF (40 mL) and Et₃N (4 mL) and

heated at 65 °C for 16 h. The crude product was purified by column

chromatography on silica gel (CH₂Cl₂/n-hexane = 2:1, v/v) to give

11 mg (0.009 mmol, 31%) of a purple solid after recrystallization

from CH₂Cl₂/MeOH; m.p. Ͼ300 °C; R_f= 0.36 (CH₂Cl₂/n-hexane

3

³J_H,H= 4.5 Hz, 2 H, H_β), 9.11–9.12 (d, J_H,H= 4.5 Hz, 2 H, H_β),

1

= 2:1, v/v). H NMR (400 MHz, CDCl₃, TMS): δ = –2.02 (s, 2 H,

3

NH), –1.92 (s, 2 H, NH), 1.16 (t, ³J = 7.6 Hz, 3 H, CH₂CH₂-

CH₂CH₃), 1.85 (m, 2 H, CH₂CH₂CH₂CH₃), 2.53 (m, 2 H,

CH₂CH₂CH₂CH₃), 5.01 (t, ³J = 8.2, 2 H, 7.6 Hz, CH₂CH₂-

9.95–9.96 (d, J_H–H= 4.8 Hz, 2 H, H_β), 10.36–10.37 (d, J_H,H

=

4.7 Hz, 2 H, H_β) ppm. UV/Vis (THF): λ_max(logε) = 407 (4.89),

471 (5.13), 520 (4.22), 625 (4.40), 712 nm (4.48) ppm. HRMS (ESI)

m/z calcd. for C₇₉H₅₂N₈O [M + H]⁺1128.4264; found 1128.4277.

3

CH₂CH₃), 7.84 (m, 12 H, Ar-H), 8.30 (d, J = 7.0 Hz, 8 H, Ar-H),

8.42 (d, ³J = 8.8 Hz, 2 H, Ar-H), 8.67 (d, ³J = 8.8 Hz, 2 H, Ar-H),

8.71 (d, ³J = 4.7 Hz, 2 H, H_β), 8.89 (dd, ³J = 4.7 Hz, 4 H, H_β),

5-[(5Ј-Hexyl-10Ј,20Ј-diphenylporphyrin-5Ј-yl)ethynyl]-10,15,20-tri-

phenylporphyrin (109): Produced from 69 (30 mg, 0.053 mmol), 18

(33 mg, 0.053 mmol), AsPh₃(34 mg, 0.111 mmol), and Pd₂(dba)₃

(5 mg, 0.004 mmol) using general procedure J to yield a dark solid

following column chromatography (silica, CH₂Cl₂/hexane, 1:3, v/v)

(23 mg, 0.340 mmol, 39%); m.p. Ͼ 300 °C. ¹H NMR (400 MHz,

CDCl₃, TMS): δ = –1.99 (s, 2 H, NH) –1.93 (s, 2 H, NH) 0.91 (t,

3 H, CH₃), 1.76–1.81 (m, 4 H, CH₂), 1.84–1.88 (m, 2 H, CH₂), 2.58

(m, 2 H, CH₂), 5.00 (m, 2 H, CH₂), 7.82 (m, 16 H, Ph-H), 8.30 (m,

12 H, Ph-H), 8.23–8.36 (m, 4 H, H_β), 8.90–8.91 (d, 2 H, H_β), 9.05–

3

9.05 (d, ³J = 4.1 Hz, 2 H, H_β), 9.11 (d, J = 4.7 Hz, 2 H, H_β), 9.48

3

(d, J = 5.3 Hz, 2 H, H_β), 10.26 (d, J = 4.7 Hz, 2 H, H_β), 10.35

3

(d, J = 4.7 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ =

14.7, 22.5, 30.7, 40.7, 99.1, 100.5, 101.5, 121.0, 121.8, 126.6, 127.7,

134.3, 134.8, 141.4 ppm. UV/Vis (CH₂Cl₂): λ_max(log ε) = 409

(5.03), 428 (5.04), 472 (5.20), 519 (4.37), 622 (4.47), 713 nm (4.54).

HRMS (MS ES⁺) m/z calcd. for [C₇₆H₅₄N₉O₂]: 1124.4384; found

1124.4400.

9.06 (d, 2 H, H_β), 9.09–9.11 (d, 2 H, H_β), 9.46–9.48 (d, 2 H, H_β), 2-(5-Butyl-10,20-dinaphthylporphyrin-5-yl)-1-[15Ј-(4-nitrophenyl)-

10.27–10.29 (d, 2 H, H_β), 10.33–10.34 (d, 2 H, H_β) ppm. ¹³C NMR 10Ј,20Ј-diphenylporphyrin-5Ј-yl]ethyne (113): Following general pro-

(150 MHz, CDCl₃): δ = 14.2, 22.8, 29.4, 29.7, 31.9, 126.8, 126.9,

cedure J, 76 (18 mg, 0.029 mmol), 28 (20 mg, 0.029 mmol), AsPh₃

127.9, 134.4, 134.5, 134.6, 141.9 ppm. UV/Vis (THF): λ_max(logε) (18 mg, 0.057 mmol), and Pd₂(dba)₃(7 mg, 0.007 mmol) were

= 427 (4.79), 472 (5.02), 519 (4.11), 620 (4.24), 714 nm (4.34). added to a mixture of THF (40 mL) and Et₃N (4 mL) and heated

Eur. J. Org. Chem. 2011, 5817–5844

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5837

M. O. Senge et al.

FULL PAPER

at 65 °C for 14 h. The crude product was purified by column

chromatography (CH₂Cl₂/n-hexane = 2:1, v/v) to give 9 mg

(0.007 mmol, 25%) of a purple solid after recrystallization from

CH₂Cl₂/MeOH; m.p. Ͼ300 °C; R_f= 0.5 (CH₂Cl₂/n-hexane = 2:1,

chromatographies on silica gel (1. n-hexane/CH₂Cl₂= 2:1, 2. n-

hexane/ethyl acetate = 3:1, v/v) and recrystallization from CH₂Cl₂/

CH₃OH to give purple crystals (18 mg, 0.016 mmol, 33%); m.p.

Ͼ300 °C; R_f= 0.5 (n-hexane/CH₂Cl₂= 1:1, v/v). ¹H NMR

(400 MHz, CDCl₃, TMS): δ = –2.06 (s, 2 H, NH), –1.97 (s, 2 H,

1

v/v). H NMR (600 MHz, CDCl₃, TMS): δ = –2.02 (s, 2 H, NH),

3

–1.62 (s, 2 H, NH), 1.15 (t, J = 7.0 Hz, 3 H, CH₂CH₂CH₂CH₃), NH), 1.00 (t, J = 7.0 Hz, 3 H, CH₂CH₂CH₂CH₂CH₂CH₃), 1.05 [t,

1.86 (m, 2 H, CH₂CH₂CH₂CH₃), 2.55 (m, 2 H, CH₂CH₂CH₂CH₃), J = 7.0 Hz, 6 H, CH(CH₂CH₃)₂], 1.47 (m, 2 H, CH₂CH₂CH₂-

3

4.95 (t, J = 8.8, 2 H, 7.6 Hz, CH₂CH₂CH₂CH₃), 7.18–7.26 (m, 4

CH₂CH₂CH₃), 1.55 (m, 2 H, CH₂CH₂CH₂CH₂CH₂CH₃), 1.89 (m,

H, Ar-H), 7.57 (m, 2 H, Ar-H), 7.79–7.84 (m, 8 H, Ar-H), 7.96 (m, 2 H , C H ₂C H ₂C H ₂C H ₂C H ₂C H ₃) , 2 . 6 2 ( m , 2 H ,

3

2 H, Ar-H), 8.22 (d, J = 8.7 Hz, 2 H, Ar-H), 8.26 (d, J = 6.4 Hz,

CH₂CH₂CH₂CH₂CH₂CH₃), 2.90 [m, 2 H, CH(CH₂CH₃)₂], 3.04

[m, 2 H, CH(CH₂CH₃)₂], 4.06 (s, 6 H, OCH₃), 4.24 (s, 3 H, OCH₃),

5.00 (t, J = 7.0 Hz, 2 H, CH₂CH₂CH₂CH₂CH₂CH₃), 5.11 [m, 1 H,

CH(CH₂CH₃)₂], 7.56 (s, 2 H, Ar-H), 7.99 (t, J = 7.6 Hz, 1 H, Ar-

H), 8.56 (d, J = 7.6 Hz, 1 H, Ar-H), 8.70 (d, J = 4.7 Hz, 1 H, H_β),

3

4 H, Ar-H), 8.38 (dd, J = 8.3 Hz, 6 H, Ar-H), 8.65 (m, 2 H, H_β),

8.68 (d, ³J = 4.5 Hz, 2 H, H_β), 8.80 (m, 2 H, H_β), 8.85 (d, ³J =

4.5 Hz, 2 H, H_β), 9.04 (d, ³J = 4.1 Hz, 2 H, H_β), 9.37 (d, ³J =

3

3.4 Hz, 2 H, H_β), 10.14 (d, J = 4.5 Hz, 2 H, H_β), 10.27 (d, J =

4.1 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 13.9, 8.72 (s, 1 H, Ar-H), 8.75 (d, J = 4.7 Hz, 1 H, H_β), 8.96 (d, 1 H,

23.5, 35.1, 40.7, 99.2, 100.2, 101.4, 118.1, 121.7, 122.9, 124.1, 125.6,

126.2, 127.8, 128.7, 129.8, 132.5, 134.8, 136.7, 139.0, 141.3, 147.7,

148.8 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 409 (4.92), 430 (4.93),

473 (5.16), 520 (4.22), 620 (4.37), 714 nm (4.45). HRMS (MS ES⁺)

m/z calcd. for [C₈₄H₅₇N₉O₂]: 1224.4655; found 1224.4662.

H_β), 9.12 (s, 1 H, Ar-H), 9.26 (d, J = 4.7 Hz, 1 H, H_β), 9.43 (br. s,

2 H, H_β), 9.47 (d, J = 4.7 Hz, 1 H, H_β), 9.56 (d, J = 4.7 Hz, 2 H,

H_β), 9.75 (d, J = 4.7 Hz, 2 H, H_β), 9.79 (br. s, 1 H, H_β), 10.27 (s,

2 H, H_meso), 10.35 (d, J = 4.1 Hz, 2 H, H_β), 10.42 (d, J = 4.7 Hz,

1 H, H_β), 10.50 (d, J = 4.7 Hz, 1 H, H_β) ppm. ¹³C NMR (150 MHz,

CDCl₃): δ = 14.0, 22.6, 31.7, 34.5, 35.3, 38.7, 50.0, 56.3, 61.1, 98.1,

99.2, 99.6, 100.7, 105.9, 112.7, 117.4, 120.7, 122.6, 125.2, 127.4,

127.6, 128.0, 128.8, 129.1, 130.7, 131.3, 131.8 ppm. UV/Vis

(CH₂Cl₂): λ_max(log ε) = 416 (5.09), 437 (4.92), 468 (5.30), 513

(4.35), 553 (4.04), 615 (4.49), 710 nm (3.61). HRMS: m/z calcd. for

(MS ES⁺) [C₆₈H₆₂N₉O₅] [M + H⁺]: 1084.4874; found 1084.4926.

2-(10,20-Diphenylporphyrin-5-yl)-1-[5-(1-ethylpropyl)porphyrin-

15-yl]ethyne (114): Following general procedure J, 77 (30 mg,

0.065 mmol), 85 (32 mg, 0.065 mmol), AsPh₃(40 mg, 0.13 mmol),

and Pd₂(dba)₃(15 mg, 0.016 mmol) in a mixture of THF (15 mL)

and NEt₃(5 mL) were used. Purification of the product was carried

out by two column chromatographies on silica gel (1. n-hexane/

CH₂Cl₂= 4:1, 2. 1:1, v/v) and recrystallization from CH₂Cl₂/

5-{[4-(10Ј,20Ј-Diphenylporphyrin-5Ј-yl)phenyl]ethynyl}-10,20-di-

CH₃OH to give purple crystals (16 mg, 0.018 mmol, 29%); m.p. phenylporphyrin (117): Following general procedure I, 29 (30 mg,

Ͼ300 °C; R_f= 0.57 (n-hexane/CH₂Cl₂= 1:1, v/v). ¹H NMR

0.0533 mmol), 9 (32 mg, 0.059 mmol), AsPh₃(33 mg, 0.106 mmol),

(400 MHz, CDCl₃, TMS): δ = –2.27 (s, 2 H, NH), –2.12 (s, 2 H, and Pd₂(dba)₃(12 mg, 0.013 mmol) in a mixture of THF (15 mL)

NH), 1.04 [t, ³J = 7.0 Hz, 6 H, CH(CH₂CH₃)₂], 2.89 [m, 2 H,

and NEt₃(5 mL) were used. Purification by column chromatog-

CH(CH₂CH₃)₂], 3.04 [m, 2 H, CH(CH₂CH₃)₂], 5.08 [m, 1 H, raphy on silica gel (CH₂Cl₂/n-hexane = 1:1, v/v) followed by

CH(CH₂CH₃)₂], 7.87 (m, 6 H Ar-H), 8.34 (m, 4 H, Ar-H), 9.01 (d, recrystallization from CH₂Cl₂/CH₃OH gave purple crystals (25 mg,

³J = 4.7 Hz, 2 H, H_β), 9.22 (d, J = 4.7 Hz, 2 H, H_β), 9.31 (d, J 0.0244 mmol, 46%); m.p. Ͼ300 °C, R_f= 0.25 (n-hexane/CH₂Cl₂=

3

= 4.7 Hz, 2 H, H_β), 9.42 (d, J = 4.7 Hz, 2 H, H_β), 9.52 (d, J = 1:1, v/v). ¹H NMR (400 MHz, CDCl₃, TMS): δ = –2.91 (s, 2 H,

4.7 Hz, 2 H, H_β), 9.75 (m, ³J = 4.7 Hz, 2 H, H_β), 10.18 (s, 1 H,

H_meso), 10.25 (s, 2 H, H_β); 10.32 (d, J = 3.5 Hz, 2 H, H_β), 10.49

NH), –2.44 (s, 2 H, NH), 7.85 (m, 12 H Ar-H), 8.31 (m, 8 H, Ar-

H), 8.47 (s, 4 H, Ar-H), 9.01 (m, 4 H, H_β), 9.08 (m, 6 H, H_β), 9.33

(d, J = 4.4 Hz, 2 H, H_β), 9.39 (d, J = 4.4 Hz, 2 H, H_β), 10.05 (d,

3

(s, 1 H, H_meso), 10.50 (s, 1 H, H_meso) ppm. ¹³C NMR (150 MHz,

CDCl₃): δ = 14.0, 34.5, 50.7, 98.3, 98.9, 100.8, 120.7, 126.8, 127.7,

131.8, 132.5, 134.5, 141.2 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 398

(4.70), 417 (4.66), 432 (4.65), 464 (4.96), 509 (4.19), 609 (4.24),

696 nm (4.27). HRMS (MS ES⁺) m/z calcd. for [C₅₉H₄₅N₈] [M +

H⁺]: 865.3767; found 865.3757.

J = 4.41 Hz, 2 H, H_β), 10.22 (s, 1 H, H_meso), 10.28 (s, 1 H, H_meso

)

ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 93.5, 96.6, 96.7, 104.8,

106.4, 119.5, 120.5, 123.4, 126.7, 127.6, 127.7, 128.6, 129.7, 131.1,

134.5, 134.8 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 413 (4.87), 433

(4.92), 511 (3.76), 571 (3.92), 571 (3.92), 602 (3.43), 662 nm (3.59).

HRMS (MS ES⁺) m/z calcd. for [C₇₂H₄₇N₈] [M + H⁺]: 1023.3910;

found 1023.3924.

2-(10,20-Diphenylporphyrin-5-yl)-1-[5Ј-(1-ethylpropyl)porphyrin-

10Ј-yl]ethyne (115): Following general procedure J, 77 (30 mg,

0.065 mmol), 86 (37 mg, 0.065 mmol), AsPh₃(40 mg, 0.131 mmol), Dizinc(II) Complex 118:^[49]Following general procedure K, 118 was

and Pd₂(dba)₃(15 mg, 0.016 mmol) in a mixture of THF (15 mL) produced from 56 (20 mg, 0.032 mmol) and 48 (19 mg,

and NEt₃(5 mL) were used. Purification by two column chromato-

grapies on silica gel (1. CH₂Cl₂/n-hexane = 1:2, 2. CH₂Cl₂/n-hexane

= 1:2, v/v) followed by recrystallization from CH₂Cl₂/CH₃OH gave

purple crystals (10 mg, 0.011 mmol, 20%); m.p. Ͼ300 °C, R_f= 0.37

(n-hexane/CH₂Cl₂= 1:1, v/v). UV/Vis (CH₂Cl₂): λ_max(logε) = 400

(4.94), 433 (4.86), 466 (5.16), 510 (4.40), 605 (4.40), 695 nm (4.41).

HRMS (MS ES⁺) m/z calcd. for [C₅₉H₄₅N₈] [M + H⁺]: 865.3767;

found 865.3763.

0.032 mmol) to yield a purple product (16 mg, 0.014 mmol, 44%);

m.p. Ͼ 300 °C. ¹H NMR (400 MHz CDCl₃/[D₅]pyridine 10:1,

TMS): δ = 7.02 (d, 2 H, C₆H₄-H), 7.54 (d, 2 H, C₆H₄-H), 7.25 (m,

2 H, Ph-H), 7.86 (m, 10 H, Ph-H), 8.32 (m, 8 H, Ph-H), 8.48 (s, 2

3

H, H_β), 9.10 (m, 4 H, H_β), 9.17 (m, 4 H, H_β), 9.41–9.42 (d, J_H–H

= 4.3 Hz, 2 H, H_β), 9.47–9.48 (d, ³J_H–H= 4.3 Hz, 2 H, H_β), 10.11–

3

10.12 (d, J_H–H= 4.6 Hz, 2 H, H_β), 10.28 (s, 1 H, H_meso), 10.35 (s,

1 H, H_meso) ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 419 (4.89), 440

(4.62), 552 (3.75), 617 nm (3.61). HRMS (MALDI-TOF) m/z calcd.

for C₇₅H₄₂N₈Zn₂[M + 1]⁺1147.2147; found 1147.2135.

20-{[5Ј-(1-Ethylpropyl)porphyrin-15Ј-yl]ethynyl}-5-hexyl-10-(3-

nitrophenyl)-15-(3,4,5-trimethoxyphenyl)porphyrin (116): Following

general procedure J, 92 (20 mg, 0.05 mmol) 5-bromo-10-hexyl-15-

(3-nitrophenyl)-20-(3,4,5-trimethoxyphenyl)porphyrin^[6](38 mg,

0.05 mmol), AsPh₃(31 mg, 0.1 mmol) and Pd₂(dba)₃(11 mg,

5-[4-(10Ј,20Ј-Diphenylporphyrin-5Ј-yl)phenylethynyl]-10,20-bis(1-eth-

ylpropyl)porphyrin (119): Produced from 29 (23 mg, 0.041 mmol)

and 12 (25 mg, 0.041 mmol) following general procedure K to yield

0.013 mmol) in a mixture of THF (15 mL) and Et₃N (5 mL) were a purple powder (green in solution) (19 mg, 0.018 mmol, 45 %);

1

used. Purification of the product was carried out by two column

m.p. Ͼ 300 °C. H NMR (600 MHz, CDCl₃, TMS): δ = –2.87 (s,

5838

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Eur. J. Org. Chem. 2011, 5817–5844

Unsymmetrical meso-Substituted Porphyrin Dimers and Arrays

2 H, NH), –1.89 (s, 2 H, NH), 1.03 (t, ³J_H,H= 14.7 Hz, 12 H, CH₃), (0.016 mmol, 37%) of a purple solid after recrystallization from

2.88 (m, 4 H, CH₂), 3.02 (m, 4 H, CH₂), 5.05 (m, 2 H, CH), 7.85 CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.36 (CH₂Cl₂/n-hexane = 1:1,

1

(m, 6 H, Ph-H), 8.31–8.34 (m, 2 H, Ph-H), 8.49 (s, 4 H, C₆H₄-H), v/v). H NMR (400 MHz, CDCl₃, TMS): δ = –2.93 (s, 2 H, NH),

3

9.04–9.05 (d, J_H,H= 4.7 Hz, 2 H, H_β), 9.09–9.12 (dd, J_H,H

=

–1.87 (s, 2 H, NH), 1.13 (t, J = 7.8, 3 H, 6.9 Hz, CH₂CH₂CH₂-

3

13.2 Hz, 4 H, H_β), 9.41–9.42 (d, J_H,H= 4.6 Hz, 2 H, H_β), 9.67– CH₃), 1.82 (m, 2 H, CH₂CH₂CH₂CH₃), 2.52 (m, 2 H,

9.68 (m, 2 H, H_β), 9.78–9.79 (m, 2 H, H_β), 10.14 (s, 1 H, H_meso),

10.15 (s, 2 H, H_β), 10.30 (s, 1 H, H_meso) ppm. ¹³C NMR (150 MHz,

CDCl₃): δ = 13.9, 29.2, 29.3, 29.5, 30.2, 31.8, 34.07, 45.6, 119.7,

122.3, 123.6, 123.0, 125.4, 126.7, 127.4, 127.6, 128.3, 129.3, 129.6,

131.2, 131.9, 132.1, 134.6, 134.8, 138.5, 139.5, 139.7, 141.6 ppm.

UV/Vis (THF): λ_max(logε) = 412 (6.05), 434 (5.99), 508 (4.97), 572

CH₂CH₂CH₂CH₃), 4.94 (t, ³J = 7.8 Hz, 2 H, CH₂CH₂CH₂CH₃),

7.20 (m, 4 H, Ar-H), 7.56 (m, 2 H, Ar-H), 7.81 (m, 6 H, Ar-H),

7.95 (t, ³J = 7.9, 2 H, 8.8 Hz, Ar-H), 8.22 (d, ³J = 7.8 Hz, 2 H, Ar-

H), 8.29 (d, ³J = 7.8 Hz, 4 H, Ar-H), 8.30–8.42 (m, 8 H, Ar-H),

8.62 (d, ³J = 4.9 Hz, 2 H, H_β), 8.72 (m, 2 H, H_β), 8.99 (d, ³J =

3.9 Hz, 2 H, H_β), 9.04 (dd, ³J = 3.9 Hz, 4 H, H_β), 9.36 (d, ³J =

(5.07), 666 nm (4.71). HRMS (MALDI) m/z calcd. for C₇₀H₅₈N₈4.9 Hz, 2 H, H_β), 9.38 (d, ³J = 3.9 Hz, 2 H, H_β), 9.79 (d, ³J =

[M]⁺1010.4784; found 1010.4736.

4.9 Hz, 2 H, H_β), 10.27 (s, 1 H, H_meso) ppm. ¹³C NMR (150 MHz,

CDCl₃): δ = 14.0, 23.5, 35.1, 40.7, 92.8, 96.4, 98.6, 104.9, 118.1,

119.6, 122.7, 123.4, 124.1, 125.6, 126.2, 127.6, 128.5, 129.7, 130.8,

131.2, 132.5, 134.6, 136.7, 139.1, 141.6, 142.7 ppm. UV/Vis

(CH₂Cl₂): λ_max(log ε) = 413 (5.05), 439 (5.12), 510 (4.04), 543

(3.87), 579 (4.20), 671 nm (3.75). HRMS (MS ES⁺) m/z calcd. for

[C₈₄H₅₈N₈]: 1179.4863; found 1179.4805.

15-Butyl-5-[4-(10Ј,20Ј-diphenylporphyrin-15Ј-(4-nitrophenyl)-5Ј-

yl)phenylethynyl]-10,20-diphenylporphyrin (120): Following general

procedure J, 26 (30 mg, 0.050 mmol), 58 (34 mg, 0.052 mmol),

AsPh₃(31 mg, 0.100 mmol), and Pd₂(dba)₃(12 mg, 0.013 mmol)

were added to a mixture of THF (40 mL) and Et₃N (4 mL) and

kept at 65 °C for 3 d. The crude product was purified by column

chromatography (CH₂Cl₂/n-hexane = 1:2, v/v), followed by a sec-

ond column chromatography on silica gel (CH₂Cl₂/n-hexane = 1:1,

v/v) to give 25 mg (0.020 mmol, 42 %) of a purple solid after

recrystallization from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.3

(CH₂Cl₂/n-hexane = 1:1, v/v). ¹H NMR (400 MHz, CDCl₃, TMS):

5-[4-(10Ј,20Ј-Diphenylporphyrin-15Ј-(4-nitrophenyl)-5-yl)phenyl-

ethynyl]-15-butyl-10,20-dinaphthylporphyrin (123): Following gene-

ral procedure J, 26 (25 mg, 0.036 mmol), 28 (25 mg, 0.036 mmol),

AsPh₃(23 mg, 0.073 mmol), and Pd₂(dba)₃(8 mg, 0.009 mmol)

were added to a mixture of THF (40 mL) and Et₃N (4 mL) and

heated at 65 °C for 3 d. The crude product was purified by column

chromatography (CH₂Cl₂/n-hexane = 2:1, v/v/), followed by a sec-

ond silica gel column (CH₂Cl₂/n-hexane = 1:2, v/v/) to yield 21 mg

(0.016 mmol, 45%) of a purple solid after recrystallization from

CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.3 (CH₂Cl₂/n-hexane = 1:1,

3

δ = –2.69 (s, 2 H, NH), –2.14 (s, 2 H, NH), 1.16 (t, J = 7.0, 3 H,

7.6 Hz, CH₂CH₂CH₂CH₃), 1.85 (m, 2 H, CH₂CH₂CH₂CH₃), 2.55

(m, 2 H, CH₂CH₂CH₂CH₃), 5.02 (t, ³J = 7.6 Hz, 2 H,

CH₂CH₂CH₂CH₃), 7.45 (m, 2 H, Ar-H), 7.65 (m, 2 H, Ar-H), 7.83

(m, 12 H, Ar-H), 8.28 (m, 8 H, Ar-H), 8.45 (s, 4 H, Ar-H), 8.69

(m, 2 H, H_β), 8.80 (m, 2 H, H_β), 8.89 (m, 2 H, H_β), 8.97 (m, 4 H,

H_β), 9.07 (m, 2 H, H_β), 9.48 (m, 2 H, H_β), 9.88 (m, 2 H, H_β) ppm.

¹³C NMR (150 MHz, CDCl₃): δ = 13.5, 24.5, 34.8, 40.9, 121.7,

125.6, 125.7, 127.1, 127.7, 128.1, 128.7, 129.9, 129.9, 134.1, 134.3,

134.9, 134.9, 135.1, 142.1 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 420

(5.01), 435 (5.08), 516 (3.93), 580 (4.12), 670 nm (3.70). HRMS

(MS ES⁺) m/z calcd. for [C₈₂H₅₇N₉O₂]: 1200.4655; found

1200.4641.

1

v/v). H NMR (400 MHz, CDCl₃, TMS): δ = –2.72 (s, 2 H, NH),

3

–1.87 (s, 2 H, NH), 1.13 (t, J = 7.0, 3 H, 7.6 Hz, CH₂CH₂CH₂-

CH₃), 1.84 (m, 2 H, CH₂CH₂CH₂CH₃), 2.55 (m, 2 H,

C H ₂C H ₂C H ₂C H ₃) , 4 . 9 5 ( t , ³J = 7 . 6 , 2 H , 8 . 2 H z ,

3

CH₂CH₂CH₂CH₃), 7.20 (m, 4 H, Ar-H), 7.57 (t, J = 8.2 Hz, 2 H,

3

Ar-H), 7.82 (m, 6 H, Ar-H), 7.96 (t, J = 8.2 Hz, 2 H, Ar-H), 8.22

(d, ³J = 8.2 Hz, 2 H, Ar-H), 8.26 (d, ³J = 7.6 Hz, 4 H, Ar-H), 8.33–

3

8.45 (m, 10 H, Ar-H), 8.62 (d, J = 4.1 Hz, 2 H, H_β), 8.68 (d, J =

3

8.8 Hz, 2 H, Ar-H), 8.71 (m, 2 H, H_β), 8.78 (d, J = 5.3 Hz, 2 H,

H_β), 8.94 (t, J = 4.1, 4 H, 4.7 Hz, H_β), 9.03 (d, J = 4.7 Hz, 2 H,

3

5-[4-(10Ј,20Ј-Diphenylporphyrin-5Ј-yl)phenylethynyl]-15-(4-nitro-

phenyl)-10,20-diphenylporphyrin (121): Follwing general procedure

J, 29 (34 mg, 0.060 mmol), 25 (40 mg, 0.060 mmol), AsPh₃(37 mg,

0.12 mmol), and Pd₂(dba)₃(14 mg, 0.015 mmol) were added to a

mixture of THF (40 mL) and Et₃N (4 mL) and heated at 65 °C for

24 h. The crude product was purified by column chromatography

(CH₂Cl₂/n-hexane = 1:1, v/v) to give 30 mg (0.026 mmol, 43%) of

a purple solid after recrystallization from CH₂Cl₂/CH₃OH; m.p.

Ͼ300 °C; R_f= 0.26 (CH₂Cl₂: n-hexane = 2:1, v/v). ¹H NMR

(400 MHz, CDCl₃, TMS): δ = –2.91 (s, 2 H, NH), –2.24 (s, 2 H,

NH), 7.84 (m, 12 H, Ar-H), 8.29 (m, 8 H, Ar-H), 8.41 (d, ³J =

3

H_β), 9.37 (d, J = 5.3 Hz, 2 H, H_β), 9.78 (d, J = 4.7 Hz, 2 H, H_β)

ppm. ¹³C NMR (150.9 MHz, CDCl₃): δ = 13.7, 23.2, 35.7, 40.4,

95.9, 116.4, 117.8, 120.4, 121.4, 122.5, 123.9, 125.3, 125.9, 126.4,

127.5, 128.2, 129.5, 132.2, 134.1, 134.7, 138.7, 141.4, 147.3 ppm.

UV/Vis (CH₂Cl₂): λ_max(logε) = 419 (5.21), 439 (5.33), 518 (4.26),

579 (4.41), 670 nm (4.03). HRMS (MS ES⁺) m/z calcd. for

[C₉₀H₆₂N₉O₂]: 1300.5026; found 1300.5034.

15-{[4-(10,20-Diphenylporphyrin-5-yl)phenyl]ethynyl}-5-(1-ethyl-

propyl)porphyrin (124): Following general procedure J, 29 (30 mg,

0.0533 mmol), 85 (33 mg, 0.05936), AsPh₃(36 mg, 0.118 mmol),

and Pd₂(dba)₃(13 mg, 0.015 mmol) in a mixture of THF (15 mL)

and NEt₃(5 mL) were used. Purification by column chromatog-

raphy on silica gel (n-hexane/CH₂Cl₂= 2:1, v/v) followed by a sec-

ond column using n-hexane/CH₂Cl₂(1:1, v/v) and recrystallization

from CH₂Cl₂/CH₃OH gave purple crystals (5 mg, 0.005 mmol,

8%); m.p. Ͼ300 °C, R_f= 0.37 (n-hexane/CH₂Cl₂= 1:1, v/v). ¹H

3

8.2 Hz, 2 H, Ar-H), 8.50 (s, 4 H, Ar-H), 8.67 (d, J = 8.2 Hz, 2 H,

3

Ar-H), 8.71 (d, J = 4.7 Hz, 2 H, H_β), 8.87 (d, J = 4.7 Hz, 2 H,

3

H_β), 9.03 (t, J = 4.7 Hz, 4 H, H_β), 9.07 (m, 4 H, H_β), 9.41 (d, J

= 4.1 Hz, 2 H, H_β), 9.99 (d, J = 4.7 Hz, 2 H, H_β), 10.30 (s, 1 H,

3

H_meso) ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 413 (5.08), 437(5.10),

510 (3.99), 543 (3.71), 579 (4.20), 670 nm (3.81).

15-Butyl-5-[4-(10Ј,20Ј-diphenylporphyrin-5Ј-yl)phenylethynyl]- NMR (400 MHz, CDCl₃): δ = –2.90 (s, 2 H, NH), –2.32 (s, 1 H,

10,20-dinaphthylporphyrin (122): Following general procedure J, 29

(32 mg, 0.057 mmol), 28 (40 mg, 0.057 mmol), AsPh₃(35 mg,

0.114 mmol), and Pd₂(dba)₃(13 mg, 0.014 mmol) were added to a

mixture of THF (40 mL) and Et₃N (4 mL) and heated at 65 °C for

36 h. The crude product was purified by column chromatography

on silica gel (CH₂Cl₂/n-hexane = 2:1, v/v), followed by a second

column purification (CH₂Cl₂: n-hexane = 2:3, v/v) to give 20 mg

NH), –2.24 (s, 1 H, NH), 1.01 [t, J = 7.0, 7.6 Hz, 6 H,

CH(CH₂CH₃)₂], 2.88 [m, 2 H, CH(CH₂CH₃)₂], 3.03 [m, 2 H,

CH(CH₂CH₃)₂], 5.1 [m, 1 H, CH(CH₂CH₃)₂], 7.84 (m, 6 H Ar-H),

8.32 (m, 4 H, Ar-H), 8.49 (s, 4 H, Ar-H), 9.04 (d, J = 4.7 Hz, 2 H,

H_β), 9.10 (m, 4 H, H_β), 9.41 (d, J = 4.7 Hz, 4 H, H_β), 9.51 (d, J =

4.7 Hz, 2 H, H_β), 9.72 (m, 1 H, H_β), 9.78 (m, 1 H, H_β), 9.99 (m, 2

H, H_β), 10.27 (s, 2 H, H_meso), 10.30 (s, 1 H, H_meso) ppm. ¹³C NMR

Eur. J. Org. Chem. 2011, 5817–5844

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5839

M. O. Senge et al.

FULL PAPER

(150 MHz, CDCl₃): δ = 34.5, 50.0, 53.2, 67.8, 92.2, 95.9, 96.4, 99.9,

104.1, 105.6, 119.6, 123.4, 125.0, 126.7, 129.8, 131.5, 132.3, 134.5,

141.6, 142.8 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 415 (5.01), 425

(5.05), 510 (3.85), 566 (4.09), 595 (3.49), 648 (3.53) nm. HRMS

(MS ES⁺) m/z calcd. for [C₆₅H₄₉N₈] [M + H⁺]: 941.4080; found

941.4088.

5,15-Bis[(10,20-diphenylporphyrin-5-yl)ethynyl]-10,20-diphenyl-

porphyrin (130): Trimer 130 was generated from 9 (40 mg,

0.074 mmol) and 70 (18.0, 0.035 mmol) following general pro-

cedure K to yield a purple/brown powder (20 mg, 0.014 mmol,

1

40%); m.p. Ͼ 300 °C. H NMR (400 MHz, CDCl₃/[D]TFA, 10:1,

TMS): δ = 8.16 (m, 12 H, Ph-H), 8.60 (m, 8 H, Ph-H), 8.71 (m, 6

3

H, Ph-H), 9.09–9.10 (dd, J_H,H= 6.6 Hz, 8 H, H_β), 9.17–9.18 (d,

10-{[4-(10,20-Diphenylporphyrin-5-yl)phenyl]ethynyl}-5-(1-ethyl-

propyl)porphyrin (125): Following general procedure J, 29 (30 mg,

0.053 mmol), 86 (40 mg, 0.131 mmol), AsPh₃(37 mg, 0.065 mmol),

and Pd₂(dba)₃(15 mg, 0.016 mmol) in a mixture of THF (15 mL)

and NEt₃(5 mL) were used. Purification by two column chromato-

graphies on silica gel (each with n-hexane/CH₂Cl₂, 2:1, v/v) and

recrystallization from CH₂Cl₂/CH₃OH gave purple crystals (16 mg,

3

³J_H,H= 4.8 Hz, 4 H, H_β), 9.54–9.55 (d, J_H,H= 4.7 Hz, 4 H, H_β),

3

10.11–10.12 (d, J_H,H= 4.7 Hz, 4 H, H_β), 10.20–10.22 (d, J_H,H

=

4.7 Hz, 4 H, H_β), 10.89 (s, 2 H, H_meso) ppm. ¹³C NMR (150 MHz,

CDCl₃/CF₃COOD, 10:1): δ = 124.6, 125.1, 127.4, 127.6, 128.4,

130.7, 131.2, 137.8, 138.1, 145.9, 146.3 ppm. UV/Vis: λ_max(logε) =

410 (4.96), 479 (4.96), 634 (4.57), 673 (4.53), 787 nm (4.45). HRMS

(MALDI) m/z calcd. for C₁₀₀H₆₂N₁₂[M + 1]⁺1431.5236; found

1431.5240.

0.017 mmol, 26%); m.p. Ͼ300 °C; R_f= 0.25 (n-hexane/CH₂Cl₂

=

1:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.89 (s, 2 H, NH),

–2.72 (s, 1 H, NH), –2.61 (s, 1 H, NH), 1.04 [t, J = 7.0 Hz, 6

H, CH(CH₂CH₃)₂], 2.9 [m, 2 H, CH(CH₂CH₃)₂], 3.06 [m, 2 H,

CH(CH₂CH₃)₂], 5.18 [m, 1 H, CH(CH₂CH₃)₂], 7.85 (m, 6 H, Ar-

H), 8.33 (m, 4 H, Ar-H), 8.50 (s, 4 H, Ar-H), 9.04 (d, J = 4.7 Hz,

2 H, H_β), 9.10 (m, 3 H, H_β), 9.38–9.46 (m, 5 H, H_β), 9.74 (br. s, 1

H, H_β), 9.80 (br. s, 1 H, H_β), 9.85 (br. s, 1 H, H_β), 9.92 (br. s, 1 H,

H_β), 10.12 (m, 1 H, H_β), 10.14 (s, 1 H, H_meso), 10.19 (b s, 1 H, H_β),

10.20 (s, 1 H, H_meso), 10.30 (s, 1 H, H_meso) ppm. ¹³C NMR

(150 MHz, CDCl₃): δ = 19.2, 34.6, 50.3, 93.7, 96.3, 100.2, 104.9,

105.7, 119.6, 123.5, 125.0, 126.7, 129.7, 130.9, 131.3, 134.5, 141.6,

142.8 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 414 (4.90), 510 (3.70),

564 (3.78), 655 nm (3.40). HRMS (MS ES⁺) m/z calcd. for

[C₆₅H₄₉N₈] [M + H⁺]: 941.4080; found 941.4088.

10,20-Diphenyl-5,15-bis{[4-(10Ј,20Ј-diphenylporphyrin-5Ј-

yl)phenyl]ethynyl}porphyrin (131): Trimer 131 was obtained from 29

(48 mg, 0.086 mmol) and 10 (25 mg, 0.040 mmol) to yield a purple

powdered product (24 mg, 0.015 mmol, 38%); m.p. Ͼ 300 °C. ¹H

NMR (600 MHz, CDCl₃/[D]TFA, 10:1, TMS): δ = 8.10 (m, 18 H,

3

Ph-H), 8.60 (m, 12 H, Ph-H), 8.79–8.80 (d, J_H,H= 7.5 Hz, 4 H,

3

C₆H₄-H), 8.83–8.85 (d, J_H,H= 4.6 Hz, 4 H, C₆H₄-H), 8.88–8.90

(d, ³J_H,H= 4.7 Hz, 4 H, H_β), 8.93–8.95 (m, 8 H, H_β), 9.10–9.11 (d,

3

³J_H,H= 4.6 Hz, 4 H, H_β), 9.50–9.51 (d, J_H,H= 4.5 Hz, 4 H, H_β),

3

9.71–9.72 (d, J_H,H= 4.5 Hz, 4 H, H_β), 10.75 (s, 2 H, H_meso) ppm.

¹³C NMR (150 MHz, CDCl₃/CF₃COOD, 10:1): δ = 128.2, 128.5,

128.6, 129.2, 130.3, 130.4, 130.6, 130.8, 132.3, 138.1, 138.3,

138.9 ppm. UV/Vis: λ_max(logε) = 412 (5.10), 446 (5.02), 508 (4.70),

602 (4.60), 634 (4.56), 710 nm (4.51). HRMS (MALDI) m/z calcd.

for [M]⁺(C₁₁₂H₇₀N₁₂) 1582.5846; found 1582.5859.

5,5Ј-(Buta-1,3-diyne-1,4-diyldibenzene-4,1-diyl)bis{[10,15-bis(1-

ethylpropyl)porphyrinato]zinc(II)} (126): Homocoupled side prod-

uct obtained as a purple powder from the synthesis of 135 (11 mg,

Dizinc(II) Complex 132: Synthesized from 56 (39 mg, 0.061 mmol)

and 46 (20 mg, 0.029 mmol) following general procedure K to yield

1

0.009 mmol, 21%); m.p. Ͼ 300 °C. H NMR (400 MHz, CDCl₃):

3

δ = 1.02 (t, J_H,H= 14.3 Hz, 24 H, CH₃), 2.88 (m, 8 H, CH₂), 3.06

1

a dark purple solid (14 mg, 0.007 mmol, 26%); m.p. Ͼ 300 °C. H

3

(m, 8 H, CH₂), 5.09 (m, 4 H, CH), 8.05–8.07 (d, J_H,H= 7.8 Hz, 4

NMR (400 MHz, CDCl₃/[D₅]pyridine 10:1, TMS): δ = 7.78 (m, 18

3

H, Ph-H), 8.28–8.30 (d, J_H,H= 7.3 Hz, 4 H, Ph-H), 9.13–9.14 (d,

3

H, Ph-H), 8.28 (d, J_H,H= 7.3 Hz, 12 H, Ph-H), 8.41 (m, 8 H,

³J_H,H= 9.1 Hz, 4 H, H_β), 9.47–9.48 (m, 4 H, H_β), 9.86 (m, 8 H,

H_β), 10.19 (s, 2 H, H_meso) ppm. ¹³C NMR (150 MHz, CDCl₃): δ =

14.1, 22.5, 29.5, 123.8, 128.5, 130.8, 130.9, 134.4 ppm. UV/Vis: λ_max

(logε) = 420 (5.63), 456 (4.75), 552 (4.40), 592 (3.86), 668 nm (4.00).

HRMS (MALDI) m/z calcd. for C₇₆H₇₀N₈Zn₂[M + 1]⁺1222.4306;

found 1222.4417.

C₆H₄-H), 8.98 (m, 8 H, H_β), 9.07 (m, 8 H, H_β), 9.36–9.37 (d, ³J_H,H

3

= 8.1 Hz, 4 H, H_β), 9.94–9.95 (d, J_H,H= 4.6 Hz, 4 H, H_β), 10.19

(s, 2 H, H_meso) ppm. ¹³C NMR (150 MHz, CDCl₃/[D₅]pyridine

10:1): δ = 45.6, 52.8, 63.2, 123.3, 127.0, 127.1, 129.3, 131.4, 131.6,

131.7, 132.1, 132.2, 132.5, 134.4, 134.6, 143.3, 149.3, 149.6 ppm.

UV/Vis: λ_max(logε) = 418 (4.05), 451 (3.79), 551 (2.95), 605 (2.75),

659 (2.97), 698 nm (1.94). HRMS (MALDI) m/z calcd. for

C₁₁₂H₆₄N₁₂Zn₃[M + 1]⁺1769.3372; found 1769.3369.

5,5Ј-(Buta-1,3-diyne-1,4-diyl)bis[5,15-bis(3,5-di-tert-butylphenyl)-

10-phenylporphyrin] (128): Using original Sonogashira condi-

tions,^[18]71 (20 mg, 0.025 mmol), 22 (16 mg, 0.025 mmol), CuI

(4 mg, 0.020 mmol), and PdCl₂(PPh₃)₂(20 mg, 0.011 mmol) were

dried in vacuo and then dissolved in degassed NEt₃(1 mL) and

THF (4 mL). After stirring the solution for 15 h at room temp. all

solvents were removed in vacuo and the residue purified by column

chromatography (silica, CH₂Cl₂/hexane, 1:1, v/v) to yield a green

solid. NMR showed that not the desired product was formed, but

64 had undergone reductive coupling to give 120; yyield 9 mg

Dinickel(II) Complex 133:^[40]Synthesized from 54 (20 mg,

0.032 mmol) and 47 (10 mg, 0.015 mmol) following general pro-

cedure K to yield an impure dark solid containing 133. HRMS

(MALDI) m/z calcd. for C₁₁₂H₆₄N₁₂Ni₃[M]⁺1750.3437; found

1750.3448.

Zinc(II) Complex 134: Produced from 56 (31 mg, 0.050 mmol) and

14 (20 mg, 0.024 mmol) according to general procedure K to yield

1

(0.006 mmol, 22%); m.p. Ͼ 300 °C. H NMR (600 MHz, CDCl₃,

1

TMS): δ = –2.00 (s, 4 H, NH), 1.59 (s, 72 H, tBu–H), 7.73–7.81

a dark green solid (13 mg, 0.006 mmol, 28%); m.p. Ͼ 300 °C. H

(m, 6 H, Ph-H), 7.85–7.87 (m, 4 H, Ph-H), 8.13–8.16 (m, 8 H, Ph- NMR (400 MHz, CDCl₃/[D₅]pyridine 10:1, TMS): δ = –1.73 (s, 2

3

H), 8.21–8.24 (m, 4 H, Ph-H), 8.79 (d, J_H,H= 4.7 Hz, 4 H, H_β),

H, NH), 7.73 (m, 12 H, Ph-H), 7.84 (m, 4 H, C₆H₄-H), 8.12–8.13

3

8.84 (d, J_H,H= 4.7 Hz, 4 H, H_β), 9.07 (d, J_H,H= 4.7 Hz, 4 H,

(d, J_H,H= 1.8 Hz, 4 H, C₆H₄-H), 8.23 (m, 8 H, Ph-H), 8.38 (m, 6

H_β), 9.96 (d, J_H,H= 4.7 Hz, 4 H, H_β) ppm. ¹³C NMR (150 MHz,

H, C₆H₃-H), 8.97 (m, 8 H, H_β), 9.01–9.02 (d, J_H,H= 4.5 Hz, 4 H,

3

CDCl₃): δ = 31.7, 35.0, 83.6, 85.7, 121.2, 123.0, 126.5, 128.3, 128.5,

129.8, 133.6, 134.2, 139.5, 140.5, 188.9 ppm. UV/Vis (CH₂Cl₂):

H_β), 9.04–9.05 (d, J_H,H= 4.6 Hz, 4 H, H_β), 9.31–9.32 (d, J_H,H=

3

4.5 Hz, 4 H, H_β), 9.90–9.91 (d, J_H,H= 4.7 Hz, 4 H, H_β), 10.14 (s,

λ_max(logε) = 446 (4.79), 476 (4.65), 526 (3.76), 610 (4.08), 708 nm 2 H, H_meso) ppm. ¹³C NMR (150 MHz, CDCl₃/[D₅]pyridine 10:1):

(4.19). HRMS (ESI) m/z calcd. for C₁₁₂H₁₁₄N₈[M + H]⁺δ = 13.9, 22.4, 31.4, 34.9, 120.0, 126.2, 127.0, 129.4, 129.8, 131.2,

1571.9406; found 1571.9456.

131.4, 131.6, 132.1, 134.5, 134.9, 143.2 ppm. UV/Vis: λ_max(logε) =

5840

www.eurjoc.org

Eur. J. Org. Chem. 2011, 5817–5844

Unsymmetrical meso-Substituted Porphyrin Dimers and Arrays

418 (4.55), 447 (4.39), 551 (3.32), 610 (3.57), 698 nm (3.35). HRMS

(MALDI-TOF) m/z calcd. for C₁₂₈H₉₈N₁₂Zn₃[M + 1]⁺1931.6620;

found 1931.662.

= 7.52, 4 H, 8.04 Hz, Ar-H), 8.16 (m, 4 H, Ar-H), 8.53 (m, 12 H,

Ar-H), 8.76 (m, 4 H, Ar-H), 9.05 (m, 12 H, Ar-H, H_β), 9.46 (d, J

3

= 4.8 Hz, 2 H, H_β), 9.57 (d, J = 4.8 Hz, 4 H, H_β), 9.61 (d, J =

3

4.8 Hz, 4 H, H_β), 10.02 (d, J = 4.8 Hz, 4 H, H_β), 10.62 (d, J =

4.8 Hz, 4 H, H_β), 10.68 (d, ³J = 4.8 Hz, 4 H, H_β), 11.40 (s, 2 H,

H_meso) ppm. UV/Vis (DMF): λ_max(logε) = 414 (5.52), 478 (5.25),

569 (4.62), 642 (4.56), 717 nm (4.66).

Dizinc(II) Complex 135: Produced from 55 (58 mg, 0.094 mmol)

and 49 (30 mg, 0.045 mmol) following general procedure K to yield

a purple product (green in solution); yield (34 mg, 0.020 mmol,

44%); m.p. Ͼ 300 °C. ¹H NMR (600 MHz, [D₈]THF, TMS): δ =

3

1.02 (t, J_H-H= 14.6 Hz, 24 H, CH₃), 2.93 (m, 12 H, CH₂), 3.16

5,15-Bis[(10,20-diphenylporphyrin-5-yl)ethynyl]-10,20-bis(3-meth-

oxyphenyl)porphyrin (141): Following general procedure K, 138

(28 mg, 0.047 mmol), 139^[13a](15 mg, 0.022 mmol), AsPh₃(14 mg,

0.04 mol), and Pd₂(dba)₃(5 mg, 0.006 mmol) were added to a mix-

ture of THF (40 mL) and Et₃N (4 mL) and kept at 65 °C for 24 h.

The crude product was purified by column chromatography eluting

first with CH₂Cl₂/n-hexane (2:1, v/v) then followed by elution with

neat CH₂Cl₂to give 7 mg (0.007 mmol, 18%) of purple solid after

recrystallization from CH₂Cl₂/MeOH; m.p. Ͼ300 °C; R_f= 0.44

(CH₂Cl₂/n-hexane = 2:1, v/v). ¹H NMR (400 MHz, CDCl₃, TMS):

δ = –3.68 (s, 4 H, NH), 6.00 (s, 12 H, OCH₃), 7.15–7.21 (m, 6 H,

3

(m, 12 H, CH₂), 5.35 (m, 6 H, CH), 8.50–8.51 (d, J_H–H= 7.6 Hz,

3

4 H, Ph-H), 8.54–8.55 (d, J_H,H= 7.6 Hz, 4 H, Ph-H), 9.12–9.14

3

(d, J_H,H= 9.2 Hz, 4 H, H_β), 9.44 (m, 4 H, H_β), 9.88–9.90 (m, 12

H, H_β), 10.10 (m, 4 H, H_β), 10.13 (s, 2 H, H_β) ppm. ¹³C NMR

(150 MHz, [D₈]THF): δ = 13.3, 20.2, 28.8, 29.6, 34.7, 45.1, 50.2,

124.9, 129.4, 129.9, 130.2, 130.5, 130.8, 131.1, 131.3, 134.8, 142.1,

144.5, 146.7, 147.7, 148.0, 148.8, 149.1, 149.3, 149.7, 151.6, 152.2,

152.4 ppm. UV/Vis: λ_max(logε) = 418 (5.41), 454 (5.32), 554 (4.22),

668 nm (4.59). HRMS (MALDI) m/z calcd. for C₁₂₈H₉₈N₁₂Zn₃

[M]⁺1732.6068; found 1732.6035.

3

Ar-H), 7.40 (d, J = 8.3 Hz, 4 H, Ar-H), 7.54 (m, 2 H, Ar-H), 7.71

Dizinc(II) Complex 136: Produced from 56 (20 mg, 0.032 mmol)

and 49 (10 mg, 0.015 mmol) following general procedure K to yield

a dark green product (bright green in solution); yield (6 mg,

0.003 mmol, 21%); m.p. Ͼ 300 °C. ¹H NMR (400 MHz, CDCl₃,

3

(t, J = 8.8, 4 H, 7.2 Hz, Ar-H), 7.86 (d, J = 7.2 Hz, 6 H, Ar-H),

3

7.89 (s, 4 H, Ar-H), 8.00 (t, J = 7.2, 2 H, 8.3 Hz, Ar-H), 8.24 (d,

³J = 8.8 Hz, 2 H, Ar-H), 8.42 (m, 4 H, H_β), 8.81 (m, 4 H, H_β),

8.99 (d, ³J = 4.4 Hz, 4 H, H_β), 9.16 (d, J = 5.0 Hz, 4 H, H_β), 9.36

3

TMS): δ = 0.98 (t, J_H-H= 14.6 Hz, 12 H, CH₃), 2.89 (m, 4 H,

(d, ³J = 4.4 Hz, 4 H, H_β), 10.27 (s, 2 H, H_meso), 10.29 (d, ³J =

CH₂), 3.07 (m, 4 H, CH₂), 5.16 (m, 2 H, CH), 7.67 (s, 4 H, C₆H₄-

H), 7.80 (m, 12 H, Ph-H), 8.29 (m, 8 H, Ph-H), 8.43–8.44 (d,

3.9 Hz, 2 H, H_β), 10.42 (d, J = 4.4 Hz, 2 H, H_β) ppm. ¹³C NMR

3

(150 MHz, CDCl₃): δ = 52.9, 104.6, 111.8, 118.5, 118.7, 122.9,

125.3, 125.8, 126.6, 127.5, 128.6, 130.7, 135.2, 140.6, 148.9, 149.7,

150.79, 156.6 ppm. UV/Vis (DMF): λ_max(logε) = 411 (5.18), 481

(4.92), 567 (4.29), 651 (4.24), 731 nm (4.42).

3

³J_H–H= 3.5 Hz, 4 H, C₆H₄-H), 9.03–9.04 (d, J_H–H= 4.6 Hz, 4 H,

3

H_β), 9.07–9.08 (d, J_H–H= 4.5 Hz, 4 H, H_β), 9.11–9.13 (d, J_H,H

=

3

4.6 Hz, 4 H, H_β), 9.38–9.39 (d, J_H,H= 4.5 Hz, 4 H, H_β), 9.79 (m,

4 H, H_β), 10.00 (m, 4 H, H_β), 10.20 (s, 2 H, H_meso) ppm. ¹³C NMR

(150 MHz, CDCl₃): δ = 14.6, 35.1, 50.8, 106.0, 126.5, 127.3, 129.7,

131.2, 132.0, 132.8, 134.0, 134.8, 135.2 ppm. UV/Vis (THF): λ_max

(logε) = 422 (5.63), 457 (5.20), 554 (4.14), 673 nm (4.20). HRMS

(MALDI) m/z calcd. for C₁₁₀H₇₆N₁₂Zn₃[M + H]⁺1732.6068;

found 1732.6035.

10,20-Bis{[4-(10Ј,20Ј-diphenylporphyrin-5Ј-yl)phenyl]ethynyl}-5,10-

porphyrin (145): Following general procedure K, 29 (47 mg,

0.084 mmol), 142^[13a](25 mg, 0.040 mmol), AsPh₃(25 mg,

0.08 mmol), and Pd₂(dba)₃(9 mg, 0.01 mmol) were added to a mix-

ture of THF (40 mL) and Et₃N (4 mL) and kept at 65 °C for 3 d.

The crude product was purified by column chromatography

(CH₂Cl₂/n-hexane = 1:2, v/v) followed by a second chromato-

graphic purification eluting with CH₂Cl₂/n-hexane (1:1, v/v) to give

11 mg (0.007 mmol, 17%) of a purple solid after recrystallization

from CH₂Cl₂/CH₃OH; m.p. Ͼ 300 °C; R_f= 0.5 (CH₂Cl₂/n-hexane

5,15-Bis{[4-(10Ј,20Ј-diphenylporphyrin-5Ј-yl)phenyl]ethynyl}-10,20-

dinaphthylporphyrin (137): Following general procedure K, 27

(30 mg, 0.042 mmol), 29 (49 mg, 0.087 mmol), AsPh₃(26 mg,

0.084 mmol), and Pd₂(dba)₃(10 mg, 0.0105 mmol) gave 15 mg

(0.009 mmol, 22%) of the target compound; m.p. Ͼ300 °C; R_f=

1

= 2:1, v/v). H NMR (400 MHz, CDCl₃, TMS): δ = –2.92 (s, 4 H,

0.54 (CH₂Cl₂: n-hexane = 2:1, v/v). H NMR (400 MHz, CDCl₃,

TMS): δ = –2.74 (s, 4 H, NH), –1.49 (s, 2 H, NH), 7.60 (t, ³J =

7.6 Hz, 2 H, Ar-H), 7.83 (s, 12 H, Ar-H), 8.00 (t, ³J = 7.6, 2 H,

NH), –1.77 (s, 2 H, NH), 7.82 (m, 22 H, Ar-H), 8.26 (m, 4 H, Ar-

H), 8.31 (m, 8 H, Ar-H), 8.49 (s, 8 H, Ar-H), 8.78 (s, 2 H, Ar-H),

9.02 (d, ³J = 4.7 Hz, 4 H, H_β), 9.08 (m, 8 H, H_β), 9.38 (d, ³J =

4.1 Hz, 4 H, H_β), 9.90 (d, ³J = 5.3 Hz, 2 H, H_β), 10.06 (s, 2 H, H_β),

10.27 (s, 2 H, H_meso) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 22.7,

29.7, 92.9, 97.2, 100.5, 105.0, 113.4, 119.8, 122.9, 123.4, 125.4,

126.9, 127.8, 128.3, 128.8, 129.6, 130.0, 130.5, 130.9, 131.1, 134.4,

134.7, 138.7, 139.8, 141.7, 143.2, 143.5, 147.3 ppm. UV/Vis

(CH₂Cl₂): λ_max(log ε) = 413 (5.33), 454 (5.15), 509 (4.36), 547

(4.13), 598 (4.34), 656 (3.81), 692 nm (3.91). HRMS (MS ES⁺) m/z

calcd. for [C₁₁₂H₇₁N₁₂]: 1583.6064; found 1583.6082.

3

8.2 Hz, Ar-H), 8.24 (d, J = 8.19 Hz, 2 H, Ar-H), 8.30 (s, 8 H, Ar-

H), 8.41 (m, 12 H, Ar-H), 8.73 (m, 4 H, Ar-H), 9.00 (d, ³J = 4.7 Hz,

3

4 H, H_β), 9.06 (dd, J = 4.7 Hz, 10 H, H_β), 9.40 (d, J = 4.1 Hz, 6

3

H, H_β), 9.83 (d, J = 4.7 Hz, 4 H, H_β), 10.29 (s, 2 H, H_meso) ppm.

¹³C NMR (150 MHz, CDCl₃): δ = 93.0, 95.3, 100.1, 101.9, 103.4,

105.5, 107.3, 110.1, 120.1, 120.2, 124.8, 126.3, 126.9, 127.3, 128.2,

129.6, 130.5, 131.1, 131.6, 135.1, 135.4, 142.5 ppm. UV/Vis

(CH₂Cl₂): λ_max(log ε) = 412 (5.36), 451 (5.24), 510 (4.56), 545

(4.43), 605 (4.64), 694 nm (3.48). HRMS (MS ES⁺) m/z calcd. for

[C₁₂₀H₇₅N₁₂]: 1683.6238; found 1683.6270.

10,20-Bis[4-(10Ј,20Ј-diphenylporphyrin-5Ј-yl)phenylethynyl]-5,10-

bis(4-methylphenyl)porphyrin (146): Following general procedure K,

29 (46 mg, 0.080 mmol), 143^[13a](25 mg, 0.038 mmol), AsPh₃

5,15-Bis[(10,20-diphenylporphyrin-5-yl)ethynyl]-10,20-dinaphthyl-

porphyrin (140): Following general procedure K, 9 (34 mg,

0.062 mmol), 139 (20 mg, 0.029 mmol), AsPh₃(18 mg, 0.058 mol), (23 mg, 0.076 mmol), and Pd₂(dba)₃(9 mg, 0.0095 mmol) were

and Pd₂(dba)₃(7 mg, 0.007 mmol) were added to a mixture of THF

(40 mL) and Et₃N (4 mL) and kept at 65 °C for 20 h. The crude

product was purified by column chromatography using as eluent

first CH₂Cl₂/n-hexane (2:1, v/v) followed by elution with neat

CH₂Cl₂, then a mixture of THF and methanol to give 6 mg

(0.007 mmol, 13%) of a purple solid; m.p. Ͼ300 °C; R_f= 0.3 (THF/

added to a mixture of THF (40 mL) and Et₃N (4 mL) and kept at

65 °C for 3 d. The crude product was purified by column

chromatography (CH₂Cl₂/n-hexane = 1:1, v/v) followed by a second

chromatographic purification eluting with CH₂Cl₂/n-hexane (2:1,

v/v) to give 10 mg (0.006 mmol, 16 %) of a purple solid after

recrystallization from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.36

1

3

n-hexane = 2:1, v/v). H NMR (400 MHz, d₁-TFA): δ = 7.96 (t, J (CH₂Cl₂/n-hexane = 2:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ =

Eur. J. Org. Chem. 2011, 5817–5844

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5841

M. O. Senge et al.

FULL PAPER

–2.91 (s, 4 H, NH), –1.75 (s, 2 H, NH), 2.78 (s, 6 H, CH₃), 7.63 (d, 3 mg (0.027 mmol, 7 %) of a purple solid after recrystallization

³J = 7.6 Hz, 4 H, Ar-H), 7.83 (m, 12 H, Ar-H), 8.15 (d, ³J = 8.2 Hz,

from CH₂Cl₂/MeOH; m.p. Ͼ 300 °C; R_f= 0.4 (CH₂Cl₂/n-hexane

1

4 H, Ph-H), 8.31 (m, 8 H, Ar-H), 8.49 (s, 8 H, Ar-H), 8.80 (s, 2 H, = 1:1, v/v). H NMR (400 MHz, [D₈]THF, TMS): δ = –2.22 (s, 4

H_β), 9.00 (d, ³J = 4.7 Hz, 2 H, H_β), 9.03 (d, ³J = 4.7 Hz, 4 H, H_β),

H, NH), 1.99 (s, 2 H, NH), 2.75 (s, 6 H, CH₃), 7.63 (d, ³J = 7.3 Hz,

3

9.08 (d, ³J = 4.7 Hz, 4 H, H_β), 9.10 (d, J = 4.7 Hz, 4 H, H_β), 9.39

2 H, Ar-H), 7.86 (m, 12 H, Ar-H), 8.12 (d, J = 7.8 Hz, 2 H, Ar-

3

(d, J = 4.7 Hz, 4 H, H_β), 9.89 (d, J = 4.7 Hz, 2 H, H_β), 10.06 (s, H), 8.19 (d, ³J = 7.8 Hz, 4 H, Ar-H), 8.34 (m, 8 H, Ar-H), 8.84

2 H, H_β), 10.28 (s, 2 H, H_meso) ppm. ¹³C NMR (150.9 MHz,

CDCl₃): δ = 21.3, 29.5, 92.7, 96.9, 100.2, 104.9, 119.5, 119.7, 123.0,

123.2, 126.7, 127.4, 127.6, 129.8, 131.3, 134.2, 134.5, 134.8, 137.6,

138.5, 141.5, 143.0 ppm. UV/Vis (CH₂Cl₂): λ_max(log ε) = 413

(5.10), 453 (4.91), 510 (4.06), 549 (3.76), 599 (4.03), 692 nm (3.48).

HRMS (MS ES⁺) m/z calcd. for [C₁₁₄H₇₅N₁₂]: 1611.6238; found

1611.6305.

(m, 6 H, H_β), 9.02 (d, J = 4.4 Hz, 6 H, H_β), 9.12 (d, J = 4.4 Hz,

3

2 H, H_β), 9.17 (d, ³J = 4.9 Hz, 2 H, H_β), 9.34 (d, ³J = 4.4 Hz, 4 H,

3

H_β), 10.23 (s, 2 H, H_meso), 10.34 (d, J = 4.9 Hz, 2 H, H_β), 10.44

(d, ³J = 4.9 Hz, 2 H, H_β) ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 403

(5.10), 422 (5.13), 469 (5.29), 514 (4.44), 612 (4.51), 700 nm (4.56).

5-(1-Ethylpropyl)-10,15,20-tris{[4-(10,20-diphenylporphyrin-5-

yl)phenyl]ethynyl}porphyrin (150): Following general procedure K,

29 (73 mg, 0.129 mmol), 82 (25 mg, 0.040 mmol), AsPh₃(40 mg,

0.129 mmol), and Pd₂(dba)₃(15 mg, 0.016 mmol) in a mixture of

THF (15 mL) and NEt₃(5 mL) were used. Purification by column

chromatography on silica gel (n-hexane/CH₂Cl₂= 1:1, v/v), fol-

lowed by recrystallization from CH₂Cl₂/CH₃OH afforded purple

crystals (6 mg, 0.002 mmol, 7%); m.p. Ͼ300 °C; R_f= 0.62 (n-hex-

ane/CH₂Cl₂= 1:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.90 (s,

6 H, NH), –1.20 (s, 2 H, NH), 1.04 [t, J = 7.0 Hz, 6 H,

CH(CH₂CH₃)₂], 2.92 [m, 2 H, CH(CH₂CH₃)₂], 3.01 [m, 2 H,

CH(CH₂CH₃)₂], 5.02 [m, 1 H, CH(CH₂CH₃)₂], 7.85 (m, 18 H, Ar-

H), 8.31 (m, 12 H, Ar-H), 8.51 (s, 4 H, Ar-H), 8.50 (s, 8 H, Ar-H),

9.03–9.11 (m, 19 H, H_β), 9.38 (m, 8 H, H_β), 9.93 (d, J = 4.7 Hz, 2

H, H_β), 10.01 (d, J = 4.7 Hz, 3 H, H_β), 10.26 (s, 1 H, H_meso), 10.28

(s, 2 H, H_meso) ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 412 (3.99),

463 (3.54), 509 (2.99), 547 (2.64), 584 (2.7), 626 (2.74), 714 nm

(2.37). HRMS (MS ES⁺) m/z calcd. for [C₁₄₅H₉₆N₁₆] [M + H⁺]:

2061.8082; found 1031.4080 (2⁺).

10,20-Bis[4-(10Ј,20Ј-diphenylporphyrin-5Ј-yl)phenylethynyl]-5,10-

dihexylporphyrin (147): Following general procedure I, 29 (46 mg,

0.082 mmol), 144^[6](25 mg, 0.039 mmol), AsPh₃(24 mg,

0.078 mmol), and Pd₂(dba)₃(9 mg, 0.009 mmol) were added to a

mixture of THF (40 mL) and Et₃N (4 mL) and kept at 65 °C for

3 d. The crude product was purified by column chromatography

(CH₂Cl₂/n-hexane = 1:2, v/v) to give 7 mg (0.004 mmol, 11%) of

a purple solid after recrystallization from CH₂Cl₂/CH₃OH; m.p.

Ͼ300 °C; R_f= 0.56 (CH₂Cl₂: n-hexane = 1:1, v/v). ¹H NMR

(400 MHz, CDCl₃, TMS): δ = –2.90 (s, 4 H, NH), –2.10 (s, 2 H,

NH), 1.02 (t, ³J = 6.4, 6 H, 7.0 Hz, CH₂CH₂CH₂CH₂CH₂CH₃),

1.44 (m, 4 H, CH₂CH₂CH₂CH₂CH₂CH₃), 1.58 (m, 4 H, CH₂CH₂-

CH₂CH₂CH₂CH₃), 1.87 (m, 4 H, CH₂CH₂CH₂CH₂CH₂CH₃), 2.56

(m, 4 H, CH₂CH₂CH₂CH₂CH₂CH₃), 4.94 (t, ³J = 8.2, 4 H, 6.4 Hz,

CH₂CH₂CH₂CH₂CH₂CH₃), 7.84 (m, 12 H, Ar-H), 8.32 (m, 8 H,

Ar-H), 8.47 (s, 8 H, Ar-H), 9.04 (d, ³J = 4.7 Hz, 4 H, H_β), 9.10

3

(dd, J = 4.7 Hz, 6 H, H_β), 9.40 (d, J = 4.7 Hz, 2 H, H_β), 9.46 (s,

2 H, H_β), 9.50 (d, ³J = 4.1 Hz, 4 H, H_β), 9.53 (d, ³J = 4.7 Hz, 2 H,

H_β), 9.93 (d, ³J = 4.1 Hz, 4 H, H_β), 10.29 (s, 2 H, H_meso) ppm. UV/

Vis (CH₂Cl₂): λ_max(logε) = 413 (5.05), 436 (5.07), 509 (4.06), 545

(3.89), 583 (4.22), 677 nm (3.96) ppm.

Dizinc Complex 151: Produced as a side product from the synthesis

of 135 under Sonogashira conditions (general procedure F). Phen-

ylethynylporphyrin 55 (48 mg, 0.078 mmol), 49 (25 mg,

0.037 mmol), CuI, and PdCl₂(PPh₃)₂yielded a purple solid (18 mg,

0.015 mmol, 40%); m.p. Ͼ 300 °C. ¹H NMR (600 MHz, CDCl₃,

10,20-Bis[4-{10Ј,20Ј-diphenylporphyrin-15Ј-(4-nitrophenyl)-5-

yl}phenylethynyl]-5,10-bis(4-methylphenyl)porphyrin (148): Follow-

ing general procedure K, 58 (53 mg, 0.077 mmol), 142^[13a](25 mg,

0.038 mmol), AsPh^[3](24 mg, 0.077 mmol), and Pd₂(dba)₃(9 mg,

0.009 mmol) were added to a mixture of THF (40 mL) and Et₃N

(4 mL) and kept at 65 °C for 24 h. The crude product was purified

by column chromatographiy (CH₂Cl₂/n-hexane = 2:1, v/v) to give

13 mg (0.007 mmol, 18%) of a purple solid after recrystallization

from CH₂Cl₂/CH₃OH; m.p. Ͼ 300 °C; R_f= 0.2 (CH₂Cl₂/n-hexane

3

TMS): δ = 1.02 (t, J_H,H= 14.5 Hz, 24 H, CH₃), 2.88 (m, 8 H,

CH₂), 3.06 (m, 8 H, CH₂), 5.21 (m, 2 H, CH), 5.23 (m, 2 H, CH),

3

7.55 (s, 1 H, Ph-H), 7.72 (s, 1 H, Ph-H), 8.04–8.06 (d, J_H,H

=

8.3 Hz, 1 H, Ph-H), 8.28–8.30 (d, ³J_H,H= 8.0 Hz, 1 H, Ph-H), 9.18–

9.20 (m, 2 H, H_β), 9.47–9.48 (m, 2 H, H_β), 9.69–9.93 (m, 10 H,

H_β), 10.07 (m, 2 H, H_β), 10.18 (s, 1 H, H_meso) ppm. ¹³C NMR

(150 MHz, CDCl₃): δ = 14.1, 14.2, 22.5, 22.8, 29.5, 34.7, 50.4,

123.4, 123.6, 125.8, 128.7, 129.4, 130.7, 131.3, 131.6, 132.8, 134.3,

134.6, 143.7, 149.4, 152.3 ppm. UV/Vis: λ_max(logε) = 418 (5.19),

444 (5.21), 554 (4.03), 640 nm (4.29). HRMS (MALDI) m/z calcd.

for C₆₈H₆₅N₈Zn₂Br [M]⁺1200.3098; found 1200.3135.

1

= 2:1, v/v). H NMR (400 MHz, CDCl₃, TMS): δ = –2.68 (s, 4 H,

3

NH), –1.74 (s, 2 H, NH), 2.79 (s, 6 H, CH₃), 7.63 (d, J = 7.6 Hz,

3

4 H, Ar-H), 7.80–7.85 (m, 12 H, Ar-H), 8.15 (d, J = 7.6 Hz, 4 H,

Ar-H), 8.28 (d, ³J = 6.4 Hz, 8 H, Ar-H), 8.43 (d, ³J = 8.2 Hz, 4 H,

3

Ar-H), 8.49 (s, 8 H, Ar-H), 8.67 (d, J = 8.2 Hz, 4 H, Ar-H), 8.79

Dizinc(II) Complex 152: Produced from 56 (39 mg, 0.063 mmol)

and 49 (20 mg, 0.030 mmol) under Sonogashira conditions (general

procedure F) to yield a purple solid (15 mg, 0.013 mmol, 42%);

m.p. Ͼ 300 °C. ¹H NMR (400 MHz, CDCl₃, TMS): δ = 0.97 (t,

³J_H,H= 14.8 Hz, 12 H, CH₃), 2.86 (m, 4 H, C₂), 3.02 (m, 4 H,

CH₂), 5.12 (m, 2 H, CH), 7.82 (m, 6 H, Ph-H), 8.32 (m, 4 H, Ph-

H), 8.45 (m, 4 H, C₆H₄-H), 9.02–9.04 (d, ³J_H,H= 4.6 Hz, 2 H, H_β),

3

(t, J = 4.8, 6 H, 4.1 Hz, H_β), 8.95 (d, J = 4.7 Hz, 4 H, H_β), 8.99

3

(d, J = 4.7 Hz, 6 H, H_β), 9.09 (d, J = 4.7 Hz, 4 H, H_β), 9.89 (d,

³J = 4.7 Hz, 2 H, H_β), 10.05 (s, 2 H, H_β) ppm. ¹³C NMR

(150 MHz, CDCl₃): δ = 21.4, 29.5, 93.0, 96.8, 100.2, 116.7, 120.0,

121.7, 123.1, 126.7, 127.8, 130.0, 134.2, 135.0, 137.6, 138.5, 141.7,

142.3, 147.6, 149.0 ppm. UV/Vis (CH₂Cl₂): λ_max(log ε) = 420

(5.31), 454 (5.12), 517 (4.34), 555 (4.19), 598 (4.26), 692 nm (3.73).

3

9.07–9.08 (d, J_H,H= 4.4 Hz, 2 H, H_β), 9.11–9.12 (d, J_H,H

=

3

10,20-Bis[(10Ј,20Ј-diphenylporphyrin-5Ј-yl)ethynyl]-5,10-bis(4-

methylphenyl)porphyrin (149): Following general procedure K, 77

4.6 Hz, 2 H, H_β), 9.37–9.38 (d, J_H,H= 4.3 Hz, 2 H, H_β), 9.71 (m,

6 H, H_β), 9.99 (s, 2 H, H_β), 10.20 (s, 1 H, H_meso) ppm. ¹³C NMR

(21 mg, 0.042 mmol), 143^[13a](10 mg, 0.020 mmol), AsPh₃(13 mg, (150 MHz, CDCl₃): δ = 14.0, 29.5, 34.7, 50.3, 120.2, 126.2, 127.1,

0.04 mmol), and Pd₂(dba)₃(4 mg, 0.004 mmol) were added to a

mixture of THF (40 mL) and Et₃N (4 mL) and kept at 65 °C for

3 d. The crude product was purified by two consecutive column

chromatographies (CH₂Cl₂: n-hexane = 1. 1:2, 2. 1:1, v/v) to yield

129.3, 130.7, 131.5, 131.7, 132.3, 134.5, 134.8, 143.1, 145.8, 149.1,

149.4, 149.7, 149.9, 150.1 ppm. UV/Vis: λ_max(logε) = 420 (5.49),

444 (5.46), 552 (4.33), 640 nm (4.54). HRMS (MALDI) m/z calcd.

for C₇₀H₅₃N₈Zn₂Br [M]⁺1212.2159; found 1212.2184.

5842

www.eurjoc.org

Eur. J. Org. Chem. 2011, 5817–5844

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Acknowledgments

This work was supported by grants from Science Foundation Ire-

land (SFI) (P.I. 09/IN.1/B2650 and SFI Ureka Supplement 04/RP1/

B482UR08) and the Health Research Board (HRB) (Translational

Research Award 2007 TRA/2007/11). We are grateful to the Centre

for Synthesis and Chemical Biology (CSCB) for HRMS measure-

ments.

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Received: May 8, 2011

Published Online: August 24, 2011

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Article Doi

Porphyrin dimers and arrays

DOI: 10.1002/ejoc.201100642

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