5,15-A2B2- and 5,15-A2BC-type porphyrins with donor and acceptor groups for use in nonlinear optics and photodynamic therapy

FULL PAPER

DOI: 10.1002/ejoc.201100641

5,15-A₂B₂- and 5,15-A₂BC-Type Porphyrins with Donor and Acceptor Groups

for Use in Nonlinear Optics and Photodynamic Therapy^[‡]

Mathias O. Senge,*^[a,b]Marijana Fazekas,^[a]Monica Pintea,^[a]Monika Zawadzka,^[a]and

Werner J. Blau^[c]

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

Keywords: Porphyrinoids / Nitrogen heterocycles / C–C coupling / Nonlinear optics / Donor–acceptor systems /

Photodynamic therapy

Development of efficient new synthetic strategies leading to

more diversified substitution patterns of porphyrin rings is of

great importance as it expands the potential applicability of

these compounds and provides a more accurate way of tailor-

ing their properties for a specific application. Changes in the

electronic and conformational structures induced by different

substituents are manifested by unique properties which are

of interest for many applications ranging from amphiphilic

porphyrins for photodynamic therapy, push–pull systems for

optical applications, chiral systems useful in catalysis, to do-

nor–acceptor systems suitable for electron transfer studies.

Different chemical strategies were demonstrated for access

to unsymetrically substituted porphyrins with nonequivalent

β or meso substituents. For the latter we have adopted the

functionalization of preformed porphyrins in order to obtain

a diverse range of porphyrin structures with 5,15-A₂B₂and

5,15-A₂BC meso substitution patterns suitable for applica-

tions in optical limiting and photodynamic therapy. The func-

tionalization of A₂-type starting materials by organolithium

and palladium-catalyzed cross-coupling reactions is an ef-

ficient means to enable the introduction of almost any de-

sired meso substituent. We report the nonlinear absorptive

properties of our A₂B₂and A₂BC porphyrins and show that

there is strong correlation between structural features and

the optical limiting efficiency. The nonlinear optical studies

indicate that the 5,15-A₂B₂substitution pattern provides

more promising candidates for use in optical limiting.

the range of accessible materials and advance these applica-

tions. Likewise, tailoring the nature of the electron-donating

and -withdrawing meso substituents is crucial for the ef-

ficient generation of ET, which mimics natural processes

and is related to solar energy conversion. Further progress

in both research areas requires easy access to varied struc-

tures, which necessitates the development of appropriate

synthetic strategies leading to unsymetrically substituted

porphyrins.

Introduction

Current developments for the introduction of meso sub-

stituents into porphyrins have given access to molecules

with induced permanent dipole moments whose strength

can be fine tuned by the electron-donating or -withdrawing

character of the incorporated groups. In these terms A₂B₂

(1) and A₂BC (2) compounds have emerged as interesting

candidates for application in optics^[1]and for electron trans-

fer (ET)^[2]studies. Push–pull molecules in general constitute

an important class of compounds for nonlinear optical

(NLO) studies for applications in photonics.^[3]Better access

to macrocyclic dyes with push–pull character will expand

[‡] Synthesis of Unsymmetrical meso-Substituted Porphyrins, 1.

Part 2: Ref.^[21]

[a] School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity

College Dublin,

Dublin 2, Ireland

Fax: +353-1-896-8536

E-mail: sengem@tcd.ie

Different synthetic approaches leading to A₂BC- and

A₂B₂-type porphyrins have been reported. The simplest way

to obtain 5,15-A₂B₂systems involves the acid-catalyzed

condensation of dipyromethane with aldehyde.^[4]Others in-

volve self-condensation of dipyrromethane-1-carbinoles or

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

Centre for Health Sciences, Trinity College Dublin, St James’s

Hospital,

Dublin 8, Ireland

[c] School of Physics, Trinity College Dublin,

Dublin 2, Ireland

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the elegant 1-acyldipyrromethane route developed by Lind-

sey et al.^[5]In practial terms, the acid-catalyzed condensa-

tion of dipyrromethane with two aldehyde units or two di-

pyromethane units with aldehyde is still the simplest way to

access 5,15-A₂BC compounds.^[6]Condensation of dipyrro-

methanedicarbinole with dipyrromethane has also been re-

ported but turned out not to be an efficient way to access

this substitution pattern.^[7]Other pathways to both substi-

tution patterns used a step-wise approach where preformed

5,15-A₂compounds were subjected to further functionali-

zation.^[8]

Progress in the use of organometallic reactions has made

it possible to prepare large sets of samples for quantitative

structure–activity relationship (QSAR) studies in optics.^[9]

This approach accelerates the progress of optical and bio-

medical uses of porphyrins as it enables identification of

key structural features enhancing certain physicochemical

properties and allows the prediction of more promising can-

didates for specific applications. Currently QSAR ap-

proaches are being developed for biomedical studies, i.e. to

predict the toxicity or biological activity of porphyrin-based

drugs for photodynamic therapy.^[10,11]Naturally, the

number of possible structures expands drastically with ac-

cess to more diversified substitution patterns.

Using our recently developed ABCD approach^[12]we de-

scribe here systematic studies on the applicability of

organolithium and palladium-catalyzed cross-coupling re-

actions for the functionalization of 5,15-A₂porphyrins to

access a range of 5,15-A₂B₂and 5,15-A₂BC target com-

pounds. We demonstrate that a rational design of the chem-

Scheme 1. Synthesis of A₂-porphyrins by condensation reactions.

Synthesis of 5,15-A₂B₂-Type Porphyrins

We first investigated the application of the Suzuki reac-

ical pathway enables the preparation of almost any desired tion, currently the most widely used organometallic cou-

compound. In additioin, we report the nonlinear absorptive pling reaction in porphyrin chemistry.^[16]This requires prep-

(NLA) properties of our compound library and correlate aration of the dibromoporphyrins 9–12 from the precursor

those properties to structural features.

porphyrins 8, a reaction easily achieved by treatment with

N-bromosuccinimide (NBS).^[17]Next, reaction of the bro-

moporphyrins with various boronic acids and catalysis by

Pd(PPh₃)₄and K₃PO₄gave the Suzuki-coupled products in

good yields (Scheme 2).

Results and Discussion

The arylboronic acids used ranged from electron poor

phenyl systems to N and S heterocycles. Although the 9-

phenanthrenyl derivatives 21–25 were synthesized in accept-

able yields their solubility is rather low, which limited their

use. The lowest yield was observed for the reaction of 10

with 2-benzothiophenylboronic acid. However, in this case,

formation of the disubstituted product 20 (21%) was ac-

companied by formation of the monosubstituted, debromi-

nated 33 (28%). Two other boronic acids showed no reac-

The preparation of A₂B₂- or A₂BC-type porphyrins

through functionalization reactions requires a step-wise ap-

proach, i.e. starting from A₂-porphyrins and subsequent in-

troduction of the B and C residues.^[12]

Synthesis of A₂-Type Porphyrins

A₂-type porphyrins are easily prepared by a [2+2] con- tivity with the porphyrins investigated. Reaction with (10-

densation using dipyrromethane and the respective alde- bromoanthracen-9-yl)boronic acid with 10 gave complete

hyde with the meso substituent.^[6,13]In terms of target com- consumption of starting material but only debrominated 3

pounds we focused here on the introduction of larger aryl could be isolated. In the case of (5-bromothiophen-2-yl)-

residues. As shown in Scheme 1 porphyrins with 1-naphthyl boronic acid no reaction occurred.

(3 and 5) and 9-phenanthrenyl (4) substituents were ob-

Next we prepared the zinc(II) porphyrins 34–37 by stan-

tained in 18–31% yield. Attempts to prepare the related bi- dard metallation reactions.^[18]These compounds were pre-

santhracenylporphyrin gave only the monosubstituted cursors for use in a Heck-type coupling reaction, a versatile

scrambling product 6 in low yield.^[14]For comparative pur- method for the introduction of olefinic residues into por-

poses we also included the well known 3-methoxy derivative phyrins.^[19]As shown in Scheme 3 the reaction is suitable

7 in our investigations.^[15]

for the preparation of 5,15-A₂B₂-type porphyrins and gave

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Porphyrins for Use in Nonlinear Optics

Scheme 3. Synthesis of A₂B₂porphyrins by Heck coupling.

Scheme 2. Synthesis of A₂B₂porphyrins by Suzuki coupling.

the target materials in moderate to good yields. The reactiv-

ity of the (3-methoxyphenyl)porphyrin 35 was higher than

that of the 1-naphthylporphyrin 34 and the best yields were

obtained with diethylvinyl phosphonate. All products

showed exclusive formation of E-isomers.

Last, but not least, the target compounds can be pre-

pared by Sonogashira coupling,^[20]which allows the direct

cross-coupling of terminal alkynes with aryl halides under

mild conditions through the use of catalytic [Pd(PPh₃)₂Cl₂]

with CuI as the cocatalyst in the presence of an aliphatic

amine. This method works well with the respective bromo-

porphyrins either in free base form or as zinc(II) complexes.

As shown in Scheme 4, the yields for the metal complexes

and the free base porphyrins are comparable. Trimethylsilyl-

protected alkynylporphyrins serve as precursors for the

preparation of conjugated oligoporphyrins.^[21]Thus, 51

bearing a TMS-protected acetylene group was subjected to

removal of TMS by treatment with tetrabutylammonium

fluoride (TBAF) in dichloromethane solution. The reaction

worked smoothly and gave porphyrin 52 in quantitative

yield.

Scheme 4. Synthesis of A₂B₂porphyrins by Sonogashira coupling.

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Synthesis of 5,15-A₂BC-Type Porphyrins

Push–pull porphyrins require a strong intramolecular di-

pole moment. Thus, 5,15-A₂BC-type porphyrins 2 where B

is electron-donating and C an electron-withdrawing group

have frequently been used for this purpose.^[22]We used

organolithium chemistry for the introduction of B.^[23]As

expected, substitution of the free base 3 with nBuLi was

easily achieved to yield 57. Reaction with NBS gave 58,

which readily underwent Suzuki coupling to yield the por-

phyrins 59–61 with electron-withdrawing C residues. Zin-

c(II) insertion into 58 to yield 62 allowed the preparation

of 63 by the Heck reaction and 64 by Sonogashira coupling

(Scheme 5).

Next, we attempted a mixed Suzuki reaction of 10 with

two different boronic acids. The first attempt involved reac-

tion of 10 with (4-methoxycarbonylphenyl)boronic acid and

(thiophen-3-yl)boronic acid in equimolar amounts. This

gave a mixture of the two A₂B₂porphyrins (5% 13 and 7%

17) and the A₂BC porphyrin 65 (16%). Likewise, similar

mixtures were obtained through reaction with 3-thiophene

boronic acid and (4-nitrophenyl)boronic acid (3% 15, 8%

17, 19% 66), (2-benzothiophenyl)boronic acid and (4-ni-

trophenyl)boronic acid (3% 20, 4% 15, 15% 67), or (2-

phenylethenyl)boronic acid and [4-(methoxycarbonyl)-

phenyl]boronic acid (9% 18, 6% 13, 14% 68). Although

separation of the three compounds was easily achieved by

column chromatography, the low yields make this method

suitable only as a “quick and dirty” approach.

Scheme 6. Reactions of 5,15-bis(3-methoxyphenyl)porphyrins. i)

Zn^II(OAc)₂, ii) Suzuki or Sonogashira, iii) phenylacetylene, CuI,

Pd(PPh₃)₂Cl₂, NEt₃, r.t.

Scheme 5. Synthesis of A₂BC porphyrins. i) Suzuki reaction, ii) Sonogashira or Heck reaction, iii) mixed Suzuki reaction with two boronic

acids.

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Reaction sequences similar to those shown in Scheme 5

were also used with 3-methoxyphenyl 7. This porphyrin was

butylated through reaction with nBuLi and then bromi-

nated in 80% yield to 69. As shown in Scheme 6, this com-

pound can undergo Suzuki or Sonogashira reaction to yield

the porphyrins 71–74 in acceptable yields. Likewise, metal-

lation with zinc(II) acetate yielded 70, which allowed the

generation of the phenylacetylene substituted porphyrin 75

in better yields compared to the free base 74.

Finally, we prepared 5,15-A₂BC porphyrins from already

available 5,15-BC-type porphyrins.^[12a]Such syntheses are

easily accomplished as the two free meso positions can be

quickly brominated with NBS followed by any of the out-

lined organometallic coupling reactions. As a test com-

pound we choose 5,15-dibromo-10-hexyl-20-(3,4,5-trimeth-

oxyphenyl)porphyrin 76.^[12a]As shown in Scheme 7, Suzuki

coupling reactions gave the respective A₂BC-type por-

phyrins 77–80 in good to excellent yields.

Figure 1. An example of open-aperture Z-scan data obtained for

62. I₀stands for onfocus intensity.

Firstly we looked at the OL efficiency of 5,15-A₂B₂sys-

tems where the A substituent was 1-naphthyl and the other

substituent was directly linked to porphyrin by a single

bond. The following trend in β_effwas observed with regard

to substituent B: 4-MeOOC–C₆H₄≈ 4-NC–C₆H₄Ͼ 3-thio-

phene ≈ 2-benzothiophene Ͼ 1-Me–indole (13 ≈ 14 Ͼ 17 ≈

20 Ͼ 19). This tendency reveals that NLA is enhanced for

compounds with strong electron-withdrawing groups. Com-

pounds with substituent B linked by multiple bonds re-

vealed better OL efficiency in reference to previously dis-

cussed compounds and this related to both free base sys-

tems and zinc porphyrins. Compound 43 is an exception,

which provided a very weak response. This may be related

to the particular electronic character of the PO(OEt)₂

group. In our considerations on the enhanced NLA in the

compounds where substituents were linked by multiple

bonds we referred to observations made by McEwan et

al.^[26]who reported that compounds in which Soret band

maxima are closer to the experimental wavelength gave a

stronger NLO response. The same is true for our com-

pounds where porphyrins with substituents linked by mul-

tiple bonds have Soret band maxima shifted towards longer

wavelengths, thus situated closed to the experimental wave-

length, gave a stronger signal than similar compounds with

singly bonded substituents.

Scheme 7. Reactions of 5,15-dibromo-10-hexyl-20-(3,4,5-trimeth-

oxyphenyl)porphyrin. i) RB(OH)₂, K₃PO₄, Pd(PPh₃)₄, THF, 12 h.

NLO Properties

The newly synthesized compounds were investigated for

For 5,15-A₂B₂compounds with a 3-methoxyphenyl

their NLA properties at 532 nm with the open Z-scan tech- group as the A substituent, 56 provided the strongest re-

nique. All of the compounds studied exhibited a drop in sponse of all the compounds studied. Compound 27 with a

transmission with intensity, which we attributed to reverse 4-cyanophenyl B substituent provided a comparable re-

saturable absorption.^[25a]Such behavior, which is of interest sponse to analogous 14 with 1-naphthyl instead of the 3-

for optical limiting (OL), arises in macrocyclic dyes upon methoxy phenyl group, although the NLA coefficient for

resonant or close to resonant excitation wavelength due to the former was smaller. This makes this compound a more

a sequential two-photon absorption process.^[24]The magni- promising candidate for OL applications. Put into other

tude of the transmission drop varied between compounds, words, the same rate of NLA could be achieved at higher

which implies structure–NLA relationships. The typical transparency at ambient light for 27. Next we compared

open Z-scan data obtained for the compounds studied are compounds with 3-methoxyphenyl and 1-naphthyl groups

presented in Figure 1. Details concerning data manipula- as the A substituent, but now in a 5,15-A₂BC substitution

tion follow standard methods reported in the literature.^[25]pattern. Here 72 and 73 with 3-methoxyphenyl residues

For the comparative studies described in the following para- outperformed those with 1-naphthyl groups 60 and 59 (Fig-

graphs, we used the effective intensity dependent NLA coef- ure 2).

ficient, β_eff, which is a parameter derived from data fitting

Amongst the 5,15-A₂BC compounds with 1-naphyl as

(see Table 1).

the A substituent (59–62), 62 provided the best response,

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Table 1. Comparison of the experimental data for the porphyrins studied, α₀= linear absorption coefficient; λ_max= Soret band maximum;

β_eff= effective intensity dependent nonlinear absorption coefficient; Im[χ⁽³⁾_eff] = imaginary part of the third-order susceptibility χ⁽³⁾

.

5,15-A₂B₂

A^[a]

B

α₀[cm^–1]

λ_max[nm]

β_eff[cmW^–1] ϫ10^–8

Im[χ⁽³⁾_eff] [esu] ϫ10^–12

13

14

17

18

19

20

48

39

43

27

56

af

am

bf

4-MeOOC-C₆H₄

4-NC-C₆H₄

3-thiophene

styrene

1-Me-indole

2-benzothiophene

C₆H₄-ethynyl

3-O₂N-C₆H₄-ethenyl

PO(OEt)₂-ethenyl

4-NC-C₆H₄

0.49

0.79

0.65

0.78

0.67

0.98

0.54

0.58

0.15

0.43

0.32

421

422

437

427

420

445

439

437

420

449

1.7Ϯ0.1

1.6Ϯ0.0

1.2Ϯ0.0

2.3Ϯ0.1

0.5Ϯ0.0

1.1Ϯ0.1

2.1Ϯ0.1

0.8Ϯ0.1

1.6Ϯ0.2

5.3Ϯ0.1

5.8Ϯ0.3

5.6Ϯ0.0

4.0Ϯ0.0

7.9Ϯ0.5

1.7Ϯ0.0

3.7Ϯ0.5

7.3Ϯ0.4

7.1Ϯ0.3

3.2Ϯ0.3

5.5Ϯ0.5

18.0Ϯ0.0

bm

TMS-ethynyl

5,15-A₂BC, B = n-C₄H₉

A^[a]

C

59

60

61

62

72

73

af

am

bf

4-O₂N-C₆H₄

4-NC-C₆H₄

4-MeOOC-C₆H₄

Br

4-NC-C₆H₄

4-O₂N-C₆H₄

0.63

0.20

0.76

0.62

0.70

0.80

423

422

425

419

420

0.8Ϯ0.0

0.5Ϯ0.0

0.7Ϯ0.0

1.8Ϯ0.1

2.1Ϯ0.1

1.9Ϯ0.2

2.7Ϯ0.1

1.5Ϯ0.1

2.3Ϯ0.2

6.1Ϯ0.4

7.1Ϯ0.4

6.5Ϯ0.5

[a] a = 1-naphthyl, b = 3-MeO–C₆H₄, f = free base compound, m = zinc-metallated compound.

4-MeOOC–C₆H₄groups in 13 or one of the 4-CN–C₆H₄

groups in 14 with n-C₄H₉gave compounds 61 and 60,

respectively. Both compounds with 4-MeOOC–C₆H₄sub-

stituents (13 and 61) exhibited stronger NLA than those

with 4-CN–C₆H₄substituents (14 and 60). Moreover, com-

pounds with a 5,15-A₂B₂substitution pattern outperform

the respective 5,15-A₂BC compounds.

In summary, our NLO studies revealed that NLA is

highly dependent not only on the nature of the meso sub-

stituents but also on the substitution pattern. Some initial

trends concerning the structure–OL efficiency relationships

were established, although further studies on unsymetrically

substituted compounds are necessary in order to fully

understand the correlations observed.

Figure 2. Optical limiting curves plotted as normalized trans-

The development of synthetic strategies for unsymmetri-

cally meso-substituted porphyrins also provides building

blocks to construct more complex structures such as por-

phyrin oligomers. A series of porphyrin dimers and trimers

possessing substituents similar to the previously discussed

monomers were synthesized^[21]and their NLA investigat-

ed.^[25a]In these compounds we varied both the meso sub-

stituents and the linker groups. In addition, for trimers both

possible regiochemical configuration patterns (with 5,10- or

5,15-linkages, respectively) gave linear and L-shaped arrays.

No apparent change in the NLO response was observed

mission vs. pulse energy density for 59, 60, 72, and 73.

which we attribute to the presence of zinc. Closed shell met-

als were reported to have a favorable effect on the NLA as

they produce an increase in the intersystem crossing rate

resulting in higher quantum yields for the triplet states.^[27]

Interestingly, compounds with very similar structural fea-

tures in a 5,15-A₂BC substitution pattern (59, 60, and 61)

revealed slightly different OL efficiency. This indicates a

strong correlation between the structural features and the

NLA of a compound. The same observation relates to 72 upon addition of further porphyrin units in reference to

and 73. A similar finding was reported by McEwan et al., monomers. β_effvalues of the dimers studied were compar-

where variation of a substituent at the para-position of able to those of the most promising monomers, though not

phenyl rings in tetrasubstituted porphyrins resulted in a exceeding that of the best monomer 56. The same was true

variation of their NLA but did not induce major changes for the L-shaped trimers. The NLA of linear trimers was

to ground state absorption features.^[28]

relatively poor. The better studied dimers showed that both

Finally we compared the responses of similar com- the type of linker and the meso substituent has an effect on

pounds from both substitution patterns. Compounds 13 the ground state and excited state absorption. Apart from

and 14 with a 5,15-A₂B₂substitution pattern were com- the influence of the particular meso substituent on the

pared with 5,15-A₂BC 61 and 60. Substitution of one of the NLA, the mutual position of these substituents contributed

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and the appropriate aldehyde (1.05–1.75 equiv.) were added. The

flask was shielded from ambient light followed by addition of TFA

(0.1 equiv.), and the reaction mixture was stirred for 18 h at room

temperature. After this time 2,3-dichloro-5,6-dicyano-1,4-benzo-

quinone (DDQ, 3 equiv.) was added and the mixture was stirred

for 1 h. The reaction was terminated by addition of triethylamine

(1 mL), and concentrated in vacuo. Typically, the reaction mixture

was filtered through a short silica gel column, eluting with CH₂Cl₂.

The solution was concentrated in vacuo and the residue purified

by column chromatography.

to the NLO response and this became evident during the

comparison of constitutional isomers. Theses studies again

highlight the strong structure–NLO properties relationship.

Conclusions

We demonstrated that the step-wise approach, where pre-

formed porphyrins are subjected to further functionaliza-

tion by organolithium or palladium-catalyzed cross cou-

pling reactions is an efficient and very flexible way to pre-

pare 5,15-A₂B₂- and 5,15-A₂BC-type compounds for op-

tical applications. The approach outlined provides access to

a great range of possible structures and enables fine tuning

of the properties that are crucial for the specific application.

As shown, NLO studies carried out on the compound li-

brary revealed that 5,15-A₂B₂porphyrins are more promis-

ing materials for OL devices than similar 5,15-A₂BC com-

pounds. Some initial trends concerning the relationship be-

tween NLA and the structural features were established for

the porphyrins studied. A similar approach to that de-

scribed here for OL is possible for the construction and

analysis of potential photosensitizers for photodynamic

cancer therapy and indication and is currently in progress

in our laboratory.

General Procedure B. Bromination of Porphyrins: The porphyrin

was dissolved in CHCl₃and cooled to 0 °C. Pyridine and NBS were

added directly to the flask (TLC control). After 10–20 min, the

reaction reached completion and was quenched with acetone. The

solvents were evaporated and the product was washed with several

portions of CH₃OH to yield a reddish purple solid.

General Procedure C. Suzuki Coupling: To a Schlenk flask was

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

der an argon atmosphere were added porphyrin (1 equiv.), aryl-

boronic acid or arylboronic ester (10–12.5 equiv.), and Pd(PPh₃)₄

(0.1 equiv.). The reaction was heated to reflux for 7–10 h (TLC con-

trol) and protected from light. After completion, the solvent was

evaporated and the residue was dissolved in CH₂Cl₂. This mixture

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

with Na₂SO₄. The organic solvent was evaporated and the crude

product was purified by flash chromatography followed by

recrystallization from CH₂Cl₂/CH₃OH to give the desired com-

pound.

General Procedure D. Zinc(II) Insertion with Zn(ac)₂: The por-

phyrin (1 equiv.) was dissolved in dry CH₂Cl₂(20 mL) and treated

with zinc acetate dihydrate (6 equiv.) dissolved in CH₃OH. The re-

action was monitored by TLC. The solvent was removed under

reduced pressure, and the residue was dissolved in CH₂Cl₂and

washed with H₂O. The solvent was removed under reduced pres-

sure and the residues solved in CH₂Cl₂and filtered through a short

silica gel column followed by recrystallization from CH₂Cl₂/

CH₃OH.

Experimental Section

General Methods: All chemicals used were of analytical grade and

purified before use. CH₂Cl₂was dried with phosphorus pentoxide

followed by distillation; THF was dried with sodium followed by

distillation. Silica gel 60 (Merck) was used for column chromatog-

raphy unless otherwise noted. Analytical TLC was carried out with

silica gel 60 plates (fluorescence indicator F₂₅₄; Merck). Melting

points are uncorrected and were measured with a Reichert Thermo-

var instrument. NMR spectra were recorded using Bruker AM 270

(270 MHz), Bruker DPX 400 (400.13 MHz for ¹H NMR and

100.61 MHz for ¹³C NMR) or Bruker AV 600 (600.13 MHz for ¹H

NMR and 150.90 MHz for ¹³C NMR) instruments. Chemical shifts

are given in ppm and referenced to the TMS signal as internal

standard. The assignment of the signals was confirmed by 2D spec-

tra (COSY, HMBC, heteronuclear multiple quantum coherence) ex-

cept for those porphyrins with low solubility. Electronic absorption

spectra were recorded with a Specord S10 instrument (Zeiss) using

CH₂Cl₂as the solvent. Mass spectra were recorded using a Varian

MAT 711 or MAT 112 S mass spectrometer using the EI technique

with a direct insertion probe and an excitation energy of 80 eV.

FAB spectra were recorded with a CH-5 DF instrument from Var-

ian. HRMS data were determined using a Micromass TOF instru-

ment fitted with an EI probe. Elemental analyses were performed

with a Perkin–Elmer 240 analyzer.

General Procedure E. Zinc(II) Insertion with ZnO: The free base

porphyrin was dissolved in dry CH₂Cl₂(20 mL) and treated with

zinc oxide. After the addition of four drops of trifluoroacetic acid

(TFA), the reaction mixture turned green and a change of color

back to red indicated completion of the reaction. The product was

separated from ZnO and most of the TFA by filtration through a

short silica column. Remaining traces of TFA were removed by

washing with H₂O. After drying with Na₂SO₄, the solvent was re-

moved in vacuo and the product was purified by column

chromatography (silica gel, CH₂Cl₂).

General Procedure F. Heck Reaction: The porphyrin was dissolved

in DMF (50 mL) under an argon atmosphere. The olefin, NaOAc,

Pd(OAc)₂and triphenylphosphane were added and the temperature

was raised to 120 °C for 16 h (TLC control). The crude product

was extracted into CH₂Cl₂and washed with H₂O. The product was

purified by silica gel column chromatography.

Starting Materials: Dipyrromethane,^[29]5,15-bis(3-methoxyphen-

yl)porphyrin^[15](7), 5,15-dibromo-10,20-bis(3-methoxyphenyl)por-

phyrin^[30](11), 5-butyl-10,20-bis(3-methoxyphenyl)porphyrin,^[15]

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 another 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/CH₃OH.

and

5,15-dibromo-10-hexyl-20-(3,4,5-trimethoxyphenyl)por-

phyrin^[12a](76) were prepared following published procedures.

General Procedure A. Condensation Method for 5,15-A₂Porphyrins:

Dry CH₂Cl₂(1 L) was placed in a three-necked flask equipped with

magnetic stirrer and gas inlet (argon). Dipyrromethane (1 equiv.)

Eur. J. Org. Chem. 2011, 5797–5816

www.eurjoc.org

5803

M. O. Senge, M. Fazekas, M. Pintea, M. Zawadzka, W. J. Blau

FULL PAPER

General Procedure H. Reaction with Organolithium Reagents: The

porphyrin was dissolved in 80 mL dry THF 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 for 1.5 h at room tem-

perature. H₂O (0.5 mL) was added and stirring continued for

15 min. DDQ (6 equiv.) in THF (10 mL) was added and the reac-

tion mixture was stirred for an additional hour. The reaction mix-

ture was filtered through silica gel, followed by evaporation of the

solvent. The crude reaction mixture was purified by column

chromatography.

7.52 mmol), and TFA (0.2 mL) were added to a solution of CH₂Cl₂

(1 L). The reaction mixture was stirred for 24 h at room tempera-

ture, followed by addition of DDQ (4.65 g, 21 mmol), and stirring

for 1 h at room temp. The crude product was purified by recrystalli-

zation from CH₂Cl₂/CH₃OH to give 50 mg (0.102 mmol, 3%) of

the monosubstituted scrambling product 6; m.p. Ͼ300 °C; R_f= 0.7

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

–3.26 (s, 2 H, NH), 7.02 (m, 4 H, Ar-H), 7.48 (m, 2 H, Ar-H), 8.35

3

(d, J = 8.2 Hz, 2 H, Ar-H), 8.52 (d, J = 4.1 Hz, 2 H, H_β), 9.00

3

(s, 1 H, Ar-H), 9.26 (d, J = 4.7 Hz, 2 H, H_β), 9.55 (s, 4 H, H_β),

10.34 (s, 2 H, H_meso), 10.36 (s, 1 H, H_meso) ppm. ¹³C NMR

(150 MHz, CDCl₃): δ = 103.97, 104.54, 114.53, 124.90, 125.60,

127.91, 128.10, 130.79, 131.54, 135.24 ppm. UV/Vis (CH₂Cl₂): λ_max

(logε) = 403 (4.92), 501 (3.76), 569 (3.36), 623 nm (2.87). HRMS

(MS ES⁺) m/z calcd. for [C₃₄H₂₃N₄] [M + H⁺]: 487.1923; found

487.1921.

5,15-Bis(1-naphthyl)porphyrin (3): Following general procedure A,

dipyrromethane (1 g, 6.84 mmol), 1-naphthaldehyde (1 mL,

7.52 mmol), and TFA (0.2 mL) were added to a solution of CH₂Cl₂

(1 L). The reaction mixture was stirred for 24 h at room tempera-

ture, followed by addition of DDQ (4.65 g, 21 mmol), and stirring

for 1 h at room temp. The crude product was purified by recrystalli-

zation from CH₂Cl₂/CH₃OH to give 360 mg (0.51 mmol, 18%) of

a purple product; m.p. Ͼ300 °C; R_f= 0.6 (CH₂Cl₂/n-hexane = 1:1,

v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.87 (s, 2 H, NH), 7.16

5,15-Dibromo-10,20-bis(9-phenanthrenyl)porphyrin (9): Following

general procedure B, 5,15-bis(9-phenanthrenyl)porphyrin (4)

(100 mg, 0.121 mmol) and NBS (80 mg, 0.45 mmol) gave 83 mg

(0.101 mmol, 68%) of a purple solid after recrystallization from

CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.4 (CH₂Cl₂/n-hexane = 2:1,

v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.32 (s, 2 H, NH), 7.15 (t,

³J = 8.8 Hz, 2 H, Ar-H), 7.22 (t, ³J = 7.8, 2 H, 6.8 Hz, Ar-H), 7.71

3

(m, 4 H, Ar-H), 7.54 (t, J = 8.7, 6.4 Hz, 2 H, Ar-H), 7.95 (m, 2

3

H, Ar-H), 8.20 (d, J = 8.2 Hz, 2 H, Ar-H), 8.36 (m, 4 H, Ar-H),

3

8.82 (d, ³J = 4.7 Hz, 4 H, H_β), 9.32 (d, J = 4.1 Hz, 4 H, H_β), 10.3

(s, 2 H, H_meso) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 105.12,

124.19, 125.58, 126.07, 127.74, 128.37, 130.93, 131.49, 132.73,

136.69 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 408 (5.02), 501 (3.81),

540 (3.21), 575 (3.37), 629 nm (2.94). HRMS (MS ES⁺) m/z calcd.

for [C₄₀H₂₇N₄] [M + H⁺]: 563.2236; found 563.2250.

3

(t, J = 7.8, 2 H, 6.8 Hz, Ar-H), 7.85 (t, J = 7.8, 2 H, 6.8 Hz, Ar-

H), 7.96 (t, ³J = 7.8 Hz, 2 H, Ar-H), 8.13 (d, J = 7.8 Hz, 2 H, Ar-

3

H), 8.56 (d, ³J = 5.9 Hz, 2 H, Ar-H), 8.74 (d, ³J = 4.9 Hz, 4 H,

H_β), 9.05 (t, ³J = 7.8 Hz, 4 H, Ar-H), 9.52 (d, ³J = 4.9 Hz, 4 H,

H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 103.29, 103.85,

118.45, 122.77, 123.08, 124.16, 126.69, 126.75, 126.91, 129.63,

131.07, 132.49, 132.71, 135.72, 136.58 ppm. UV/Vis (CH₂Cl₂): λ_max

(logε) = 429 (5.14), 528 (4.03), 566 (3.80), 605 (3.68), 666 nm (3.50).

HRMS: m/z calcd. for [C₄₈H₂₈N₄Br₂]: 818.0681; found 818.0638.

C₄₈H₂₈N₄Br₂(820.59): calcd. C 70.26, H 3.44, N 6.83; found C

70.45, H 3.66, N 6.74.

5,15-Bis(9-phenanthrenyl)porphyrin (4): Following general pro-

cedure A, dipyrromethane (1 g, 6.84 mmol), phenanthrene-9-carb-

aldehyde (1.48 g, 7.18 mmol), and TFA (0.2 mL) were added to a

solution of CH₂Cl₂(1 L). The reaction mixture was stirred for 24 h

at room temperature, followed by addition of DDQ (4.8 g,

21 mmol), and stirring for 1 h at room temp. The crude product

was purified by recrystallization from CH₂Cl₂/CH₃OH to give

340 mg (0.51 mmol, 15%) of a purple product; m.p. Ͼ300 °C; R_f=

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

= –2.81 (s, 2 H, NH), 7.18 (m, 4 H, Ar-H), 7.54 (s, 2 H, Ar-H),

5,15-Dibromo-10,20-bis(1-naphthyl)porphyrin (10): Following gene-

ral procedure B, 5,15-bis(1-naphthyl)porphyrin (3) (260 mg,

0.46 mmol) and NBS (205 mg, 1.15 mmol) gave 250 mg

(0.35 mmol, 75%) of a purple solid after recrystallization from

CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.25 (CH₂Cl₂/n-hexane = 1:1,

v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.40 (s, 2 H, NH), 7.09 (t,

3

7.69 (d, J = 8.8 Hz, 2 H, Ar-H), 7.86 (m, 2 H, Ar-H), 7.97 (d, J

3

= 7.6 Hz, 2 H, Ar-H), 8.17 (d, J = 6.4 Hz, 2 H, Ar-H), 8.65 (m, 4

H, Ar-H), 8.93 (d, J = 4.1 Hz, 4 H, H_β), 9.08 (d, J = 4.7 Hz, 2

H, H_β), 9.32 (d, J = 5.3 Hz, 2 H, H_β), 10.32 (s, 2 H, H_meso) ppm.

3

³J = 7.6, 2 H, 8.2 Hz, Ar-H), 7.15 (m, 2 H, Ar-H), 7.55 (t, J = 7,

3

2 H, 7.6 Hz, Ar-H), 7.92 (t, J = 7, 2 H, 8.2 Hz, Ar-H), 8.20 (d, J

UV/Vis (CH₂Cl₂): λ_max(logε) = 411 (4.98), 502 (3.85), 542 (3.38),

575 (3.48), 637 nm (3.08). HRMS (MS ES⁺) m/z calcd. for

[C₄₈H₃₁N₄] [M + H⁺]: 663.2549; found 663.2578.

3

= 8.2 Hz, 2 H, Ar-H), 8.26 (m, 2 H, Ar-H), 8.36 (d, J = 8.2 Hz, 2

3

H, Ar-H), 8.61 (d, J = 4.7 Hz, 4 H, H_β), 9.53 (d, J = 4.7 Hz, 4

H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 103.24, 118.57,

123.80, 125.40, 125.43, 126.02, 127.49, 127.98, 128.58, 132.02,

132.33, 132.37, 132.44, 136.26, 136.28, 138.07 ppm. UV/Vis

(CH₂Cl₂): λ_max(logε) = 426 (5.08), 522 (3.93), 556 (3.67), 601

(3.49), 658 nm (3.43). HRMS (MS ES⁺) m/z calcd. for

[C₄₀H₂₅N₄Br₂] [M + H⁺]: 719.0446; found 719.0430.

5,15-Bis(4-methoxy-1-naphthyl)porphyrin (5): Following general

procedure A, dipyrromethane (1.2 g, 8 mmol), 4-methoxynaphth-

aldehyde (2.7 g, 14 mmol), and TFA (0.3 mL) were added to a solu-

tion of CH₂Cl₂(1 L). The reaction mixture was stirred for 24 h at

room temperature, followed by addition of DDQ (4.8 g, 24 mmol),

and stirring for 1 h at room temp. The crude product was purified

by recrystallization from CH₂Cl₂/CH₃OH to give 800 mg

(1.28 mmol, 31%) of a purple product; m.p. Ͼ300 °C; R_f= 0.3

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

–2.89 (s, 2 H, NH), 4.35 (s, 6 H, OCH₃), 7.14 (m, 6 H, Ar-H), 7.55

(m, 2 H, Ar-H), 8.22 (d, ³J = 8.2 Hz, 1 H, Ar-H), 8.26 (d, ³J =

5,15-Dibromo-10,20-bis(4-methoxy-1-naphthyl)porphyrin (12): Fol-

lowing general procedure B, 5,15-bis(4-methoxy-1-naphthyl)por-

phyrin (5) (360 mg, 0.58 mmol) and NBS (258 mg, 1.445 mmol)

gave 350 mg (0.45 mmol, 77%) of a purple solid after recrystalli-

zation from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.6 (CH₂Cl₂/n-

hexane = 2:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.41 (s, 2

H, NH), 4.34 (s, 6 H, OCH₃), 7.05 (m, 2 H, Ar-H), 7.17 (m, 2 H,

Ar-H), 7.25 (m, 2 H, Ar-H), 7.53 (t, ³J = 7.6, 2 H, 7 Hz, Ar-H),

3

7.6 Hz, 1 H, Ar-H), 8.62 (d, J = 8 Hz, 2 H, Ar-H), 8.66 (d, J =

4.1 Hz, 4 H, H_β), 9.30 (d, ³J = 4.7 Hz, 4 H, H_β), 10.28 (s, 2 H,

H_meso) ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 413 (5.14), 505 (4.16),

541 (3.81), 577 (3.86), 637 nm (3.58). HRMS (MS ES⁺) m/z calcd.

for [C₄₂H₃₁N₄O₂] [M + H⁺]: 623.2447; found 623.2444.

3

8.15 (t, J = 7.6, 2 H, 7 Hz, Ar-H), 8.62 (d, J = 8.8 Hz, 2 H, Ar-

H), 8.66 (d, ³J = 4.7 Hz, 4 H, H_β), 9.52 (d, ³J = 4.7 Hz, 4 H,

H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 55.73, 102.52, 119.08,

121.73, 124.62, 126.73, 128.13, 130.60, 132.70, 137.46, 156.02 ppm.

5-(9-Anthracenyl)porphyrin (6): Following general procedure A, di-

pyrromethane (1 g, 6.84 mmol), 9-anthracenecarbaldehyde (1.55 g,

5804

www.eurjoc.org

Eur. J. Org. Chem. 2011, 5797–5816

Porphyrins for Use in Nonlinear Optics

1

UV/Vis (CH₂Cl₂): λ_max(logε) = 428 (4.98), 523 (3.97), 559 (3.70), CH₃OH; m.p. Ͼ300 °C; R_f= 0.5 (CH₂Cl₂/n-hexane = 1:1, v/v). H

603 (3.50), 661 nm (3.47). HRMS (MS ES⁺) m/z calcd. for

NMR (400 MHz, CDCl₃): δ = –2.60 (s, 2 H, NH), 7.15 (m, 4 H,

Ar-H), 7.53 (t, J = 7.6 Hz, 2 H, Ar-H), 7.89 (m, 6 H, Ar-H), 8.08

3

[C₄₂H₂₉N₄O₂Br₂] [M + H⁺]: 781.0637; found 781.0599.

(d, ³J = 7.6 Hz, 4 H, Ar-H), 8.18 (d, ³J = 8.2 Hz, 2 H, Ar-H), 8.32

(m, 4 H, Ar-H), 8.63 (d, ³J = 4.7 Hz, 4 H, H_β), 8.75 (d, ³J = 4.7 Hz,

4 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 117.56, 118.20,

122.03, 123.79, 124.74, 125.28, 126.92, 127.45, 128.37, 129.45,

130.54, 131.65, 132.27, 132.43, 135.34, 136.32, 138.69, 140.35 ppm.

UV/Vis (CH₂Cl₂): λ_max(logε) = 422 (5.22), 515 (3.97), 548 (3.53),

592 (3.46), 644 nm (3.22). HRMS: m/z calcd. for (MS ES⁺)

[C₅₂H₃₃N₄Br₂] [M + H⁺]: 873.1051; found 873.1013.

5,15-Bis(4-methoxycarbonylphenyl)-10,20-bis(1-naphthyl)porphyrin

(13): Following general procedure C, 5,15-dibromo-10,20-bis(1-

naphthyl)porphyrin (10) (40 mg, 0.055 mmol), (4-methoxycarbon-

ylphenyl)boronic acid (198 mg, 1.1 mmol), Pd(PPh₃)₄(6.4 mg,

0.0055 mmol), and K₃PO₄(471 mg, 2.22 mmol) in THF (30 mL)

gave 14 mg (0.016 mmol, 30%) of a purple solid after recrystalli-

zation from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.5 (CH₂Cl₂/n-

hexane = 1:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.59 (s, 2

3

H, NH), 4.02 (s, 6 H, COOCH₃), 7.05 (m, 4 H, Ar-H), 7.44 (t, J

5,15-Bis(1-naphthyl)-10,20-bis(3-thiophenyl)porphyrin (17): Follow-

ing general procedure C, 5,15-dibromo-10,20-bis(1-naphthyl)por-

phyrin (10) (100 mg, 0.138 mmol), (thiophen-3-yl)boronic acid

(221 mg, 1.725 mol), Pd(PPh₃)₄(16 mg, 0.0138 mmol), and K₃PO₄

(737 mg, 3.47 mmol) in THF (50 mL) gave 65 mg (0.089 mmol,

65%) of a purple solid after recrystallization from CH₂Cl₂/

= 7.3, 2 H, 7.8 Hz, Ar-H), 7.82 (t, ³J = 8.3, 2 H, 6.8 Hz, Ar-H),

3

8.08 (t, J = 8.3 Hz, 2 H, Ar-H), 8.22 (m, 8 H, Ar-H), 8.34 (d, J

3

= 7.8 Hz, 4 H, Ar-H), 8.54 (d, J = 4.9 Hz, 4 H, H_β), 8.63 (d, J =

4.9 Hz, 4 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 52.43,

118.16, 118.97, 119.04, 124.26, 125.76, 126.34, 127.27, 127.93,

128.46, 128.59, 128.85, 129.62, 129.70, 130.23, 131.42, 132.75,

132.80, 132.90, 134.51, 136.78, 136.81, 139.11, 144.37, 146.69,

146.79, 166.83, 167.28 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 421

(5.19), 515 (3.89), 553 (3.41), 594 (3.38), 645 nm (3.15). HRMS

(MS ES⁺) m/z calcd. for [C₅₆H₃₉N₄O₄] [M + H⁺]: 831.2971; found

831.2957.

1

CH₃OH; m.p. Ͼ300 °C; R_f= 0.6 (CH₂Cl₂/n-hexane = 1:1, v/v). H

NMR (400 MHz, CDCl₃): δ = –2.43 (s, 2 H, NH), 7.15 (m, 4 H,

3

Ar-H), 7.52 (t, J = 7.2, 2 H, 7.5 Hz, Ar-H), 7.70 (d, J = 7 Hz, 2

3

H, Ar-H), 7.91 (t, J = 6, 2 H, 6.4 Hz, Ar-H), 8.00 (m, 4 H, Ar-

H), 8.18 (d, J = 8.3 Hz, 2 H, Ar-H), 8.32 (m, 4 H, Ar-H), 8.61 (d,

3

³J = 4.7 Hz, 4 H, H_β), 8.90 (d, ³J = 4.7 Hz, 4 H, H_β) ppm. ¹³C

NMR (150 MHz, CDCl₃): δ = 13.93, 22.48, 31.42, 114.50, 117.58,

123.33, 124.06, 125.53, 126.07, 127.70, 128.12, 128.55, 132.58,

132.74, 134.26, 136.66, 139.21, 141.83 ppm. UV/Vis (CH₂Cl₂): λ_max

(logε) = 422 (5.11), 516 (3.93), 552 (3.67), 592 (3.60), 649 nm (3.52).

HRMS (MS ES⁺) m/z calcd. for [C₄₈H₃₁N₄S₂] [M + H⁺]: 727.1990;

found 727.1981.

5,15-Bis(4-cyanophenyl)-10,20-bis(1-naphthyl)porphyrin (14): Fol-

lowing general procedure C, 5,15-dibromo-10,20-bis(1-naphthyl)-

porphyrin (10) (100 mg, 0.138 mmol), (4-cyanophenyl)boronic acid

(254 mg, 1.725 mmol), Pd(PPh₃)₄(16 mg, 0.0138 mmol), and

K₃PO₄(737 mg, 3.47 mmol) in THF (50 mL) gave 70 mg

(0.092 mmol, 66%) of a purple solid after recrystallization from

CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.5 (CH₂Cl₂/n-hexane = 1:1,

v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.52 (s, 2 H, NH), 7.13

(m, 4 H, Ar-H), 7.54 (m, 2 H, Ar-H), 7.92 (t, ³J = 7.6 Hz, 2 H, Ar-

H), 8.05 (d, ³J = 8.2 Hz, 4 H, Ar-H), 8.19 (d, ³J = 8.2 Hz, 2 H,

Ar-H), 8.33 (m, 8 H, Ar-H), 8.67 (s, 8 H, H_β) ppm. ¹³C NMR

(150 MHz, CDCl₃): δ = 55.42, 102.06, 111.54, 117.46, 118.15,

124.62, 125.93, 127.99, 128.00, 131.46, 132.33, 132.45, 136.29,

138.36, 146.26, 146.37 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 422

(5.20), 515 (3.95), 548 (3.45), 592 (3.41), 646 nm (3.13). HRMS

(MS ES⁺) m/z calcd. for [C₅₄H₃₃N₆] [M + H⁺]: 765.2767; found

765.2790.

5,15-Bis(1-naphthyl)-10,20-bis(2-phenylethenyl)porphyrin (18): Fol-

lowing general procedure C, 5,15-dibromo-10,20-bis(1-naphthyl)-

porphyrin (10) (40 mg, 0.055 mmol), trans-β-styrylboronic acid

(82 mg, 0.55 mmol), Pd(PPh₃)₄(6.4 mg, 0.0055 mmol), and K₃PO₄

(235 mg, 1.11 mmol) in THF (30 mL) gave 20 mg (0.026 mmol,

48%) of a purple solid after recrystallization from CH₂Cl₂/

1

CH₃OH; m.p. Ͼ300 °C; R_f= 0.5 (CH₂Cl₂/n-hexane = 1:1, v/v). H

NMR (400 MHz, CDCl₃): δ = –1.93 (s, 2 H, NH), 7.15 (m, 4 H,

3

Ar-H), 7.39 (d, J = 15.8 Hz, 2 H, alkene-H), 7.46 (t, J = 7.5, 2

H, 7.3 Hz, Ar-H), 7.55 (m, 6 H, Ar-H), 7.92 (d, ³J = 7 Hz, 6 H,

3

Ar-H), 8.20 (d, J = 8 Hz, 2 H, Ar-H), 8.33 (m, 4 H, Ar-H), 8.62

3

(d, J = 4.8 Hz, 4 H, H_β), 9.38 (d, J = 4.8 Hz, 4 H, H_β), 9.58 (d,

³J = 15.8 Hz, 2 H, alkene-H) ppm. ¹³C NMR (150 MHz, CDCl₃):

δ = 116.98, 118.07, 124.30, 125.73, 126. 28, 126.93, 127.91, 128.64,

129.04, 131.51, 132.62, 132.92, 136.76, 137.92, 139.50, 143.22 ppm.

UV/Vis (CH₂Cl₂): λ_max(logε) = 440 (5.11), 585 (4.01), 677 nm

(3.82). HRMS (MS ES⁺) m/z calcd. for [C₅₆H₃₉N₄] [M + H⁺]:

767.3175; found 767.3159.

5,15-Bis(1-naphthyl)-10,20-bis(4-nitrophenyl)porphyrin (15): Follow-

ing general procedure C, 5,15-dibromo-10,20-bis(1-naphthyl)por-

phyrin (10) (25 mg, 0.035 mmol), (4-nitrophenyl)boronic pinacol

ester (87 mg, 0.35 mmol), Pd(PPh₃)₄(4 mg, 0.0035 mmol), and

K₃PO₄(148 mg, 0.70 mmol) in THF (20 mL) gave 20 mg

(0.024 mmol, 71%) of a purple solid after recrystallization from

CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.5 (CH₂Cl₂/n-hexane = 1:1,

v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.50 (s, 2 H, NH), 7.12

5,15-Bis(1-methyl-1H-indol-5-yl)-10,20-bis(1-naphthyl)porphyrin

(19): Following general procedure C, 5,15-dibromo-10,20-bis(1-

naphthyl)porphyrin 10 (30 mg, 0.041 mmol), (1-methylindol-5-yl)-

boronic acid (106 mg, 0.41 mmol), Pd(PPh₃)₄(5 mg, 0.0041 mmol),

and K₃PO₄(176 mg, 0.832 mmol) in THF (30 mL) gave 15 mg

(0.018 mmol, 45%) of a purple solid after recrystallization from

CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.5 (CH₂Cl₂/n-hexane = 1:1,

v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.37 (s, 2 H, NH), 4.05 (s,

6 H, CH₃), 6.69 (m, 2 H, Ar-H) 7.14 (m, 2 H, Ar-H), 7.22 (m, 2

3

(m, 4 H, Ar-H), 7.54 (t, J = 6.4 Hz, 2 H, Ar-H), 7.92 (t, J = 7.6,

3

2 H, 8.2 Hz, Ar-H), 8.19 (d, J = 8.2 Hz, 2 H, Ar-H), 8.30 (t, J =

3

7.6 Hz, 2 H, Ar-H), 8.35 (d, J = 8.2 Hz, 2 H, Ar-H), 8.40 (m, 4

H, Ar-H), 8.62 (m, 4 H, Ar-H), 8.68 (m, 8 H, H_β) ppm. UV/Vis

(CH₂Cl₂): λ_max(logε) = 424 (5.09), 516 (3.87), 552 (3.38), 592

(3.40), 648 nm (3.19). HRMS: m/z calcd. for [C₅₂H₃₂N₆O₄]:

804.2485; found 804.2511. C₅₂H₃₂N₆O₄(804.86): calcd. C 77.60, H

4.01, N 10.44; found C 77.35, H 3.75, N 10.13.

3

5,15-Bis(4-bromophenyl)-10,20-bis(1-naphthyl)porphyrin (16): Fol-

lowing general procedure C, 5,15-dibromo-10,20-bis(1-naphthyl)-

porphyrin (10) (50 mg, 0.07 mmol), (4-bromophenyl)boronic acid

H, Ar-H), 7.32 (d, J = 7.3 Hz, 2 H, Ar-H), 7.50 (m, 2 H, Ar-H),

3

7.62 (d, J = 8.3 Hz, 2 H, Ar-H), 7.88 (t, J = 7.5 Hz, 2 H, Ar-H),

3

8.13 (m, 4 H, Ar-H), 8.30 (d, J = 7.8 Hz, 4 H, Ar-H), 8.44 (s, 2

(176 mg, 0.875 mol), Pd(PPh₃)₄(8 mg, 0.007 mmol), and K₃PO₄H, Ar-H), 8.55 (d, ³J = 4.8 Hz, 4 H, H_β), 8.79 (d, ³J = 4.8 Hz, 4 H,

(367 mg, 1.73 mmol) in THF (30 mL) gave 49 mg (0.056 mmol,

82%) of a purple solid after recrystallization from CH₂Cl₂/

H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 33.17, 101.08, 106.75,

117.09, 121.30, 124.03, 126.00, 127.02, 127.61, 128.35, 128.86,

Eur. J. Org. Chem. 2011, 5797–5816

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5805

M. O. Senge, M. Fazekas, M. Pintea, M. Zawadzka, W. J. Blau

FULL PAPER

129.77, 130.46, 132.70, 133.01, 136.18, 136.70, 139.59 ppm. UV/Vis

(4.98), 516 (3.85), 552 (3.51), 590 (3.49), 648 nm (3.32). HRMS: m/z

(CH₂Cl₂): λ_max(logε) = 427 (5.15), 519 (4.04), 555 (3.78), 592 calcd. for [C₆₂H₃₆N₆] [M + H⁺]: calcd. 840.3001; found 840.3124.

(3.73), 645 nm (3.56). HRMS (MS ES⁺) m/z calcd. for [C₅₈H₄₁N₆]

5,15-Bis(4-nitrophenyl)-10,20-bis(9-phenanthrenyl)porphyrin

(23):

[M + H⁺]: 821.3393; found 821.3373.

Following general procedure C, 5,15-dibromo-10,20-bis(9-phen-

anthrenyl)porphyrin (9) (50 mg, 0.0611 mmol), (4-nitrophenyl)-

boronic acid pinacol ester (190 mg, 0.763 mmol), Pd(PPh₃)₄(7 mg,

0.00611 mmol), and K₃PO₄(325 mg, 1.53 mmol) in THF (30 mL)

gave 30 mg (0.033 mmol, 55%) of a purple solid after recrystalli-

zation from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.5 (CH₂Cl₂/n-

hexane = 1:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.42 (s, 2

5,15-Bis(1-naphthyl)-10,20-bis(2-thianaphthyl)porphyrin (20): Fol-

lowing general procedure C, 5,15-dibromo-10,20-bis(1-naphthyl)-

porphyrin (10) (30 mg, 0.041 mmol), (thianaphthen-2-yl)boronic

acid (73 mg, 0.41 mol), Pd(PPh₃)₄(5 mg, 0.0041 mmol), and K₃PO₄

(176 mg, 0.832 mmol) in THF (30 mL) gave two compounds after

column chromatography on silica gel. The title compound 20 was

obtained as 7 mg (0.008 mmol, 21%) of purple a solid after

recrystallization from CH₂Cl₂/CH₃OH accompanied by the mono-

substituted compound 33; m.p. Ͼ300 °C; R_f= 0.66 (CH₂Cl₂/n-hex-

ane = 1:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.36 (s, 2 H,

3

H, NH), 7.18 (m, 4 H, Ar-H), 7.71 (t, J = 6.4, 2 H, 7.02 Hz, Ar-

3

H), 7.85 (t, J = 7, 2 H, 7.6 Hz, Ar-H), 7.95 (t, J = 7.6 Hz, 2 H,

Ar-H), 8.12 (d, ³J = 7.6 Hz, 2 H, Ar-H), 8.41 (d, J = 8.2 Hz, 4 H,

Ar-H), 8.61 (m, 6 H, Ar-H), 8.69 (d, J = 4.1 Hz, 4 H, H_β), 8.82

3

(d, J = 4.7 Hz, 4 H, H_β), 9.07 (t, J = 7.6 Hz, 4 H, Ar-H) ppm.

¹³C NMR (150 MHz, CDCl₃): δ = 117.11, 118.18, 121.47, 122.22,

126.04, 126.87, 127.09, 128.65, 129.25, 130.36, 131.33, 133.36,

134.56, 135.76, 136.81, 147.32, 148.16 ppm. UV/Vis (CH₂Cl₂): λ_max

(logε) = 426 (5.16), 517 (3.98), 552 (3.40), 592 (3.36), 646 nm (2.82).

HRMS: m/z calcd. for [C₆₀H₃₆N₆O₄]: 880.2798; found 880.2532.

NH), 7.13–7.16 (m, 4 H, Ar-H), 7.54 (m, 2 H, Ar-H) 7.61 (dd, J

= 7.6, 8.2 Hz, 4 H, Ar-H), 7.90 (t, ³J = 8.8, 2 H, 6.4 Hz, Ar-H),

3

8.08 (t, J = 7.6, 4 H, 6.4 Hz, Ar-H), 8.14 (s, 2 H, Ar-H), 8.18 (d,

³J = 8.8 Hz, 2 H, Ar-H), 8.31 (dd, ³J = 8.2, 7 Hz, 4 H, Ar-H), 8.61

3

(d, J = 4.1 Hz, 4 H, H_β), 9.07 (d, J = 4.7 Hz, 4 H, H_β) ppm. ¹³C

NMR (150 MHz, CDCl₃): δ = 111.49, 118.50, 121.49, 123.83,

124.08, 124.73, 124.92, 125.60, 126.19, 127.74, 128.70, 130.73,

132.58, 132.75, 136.59, 138.85, 139.17, 141.74, 142.80 ppm. UV/Vis

(CH₂Cl₂): λ_max(logε) = 428 (4.95), 519 (3.87), 557 (3.66), 592

(3.58), 648 nm (3.45). HRMS (MS ES⁺) m/z calcd. for

[C₅₆H₃₅N₄S₂] [M + H⁺]: 827.2303; found 827.2303.

5,15-Bis(9-phenanthrenyl)-10,20-bis(3-thiophenyl)porphyrin

(24):

Following general procedure C, 5,15-dibromo-10,20-bis(9-phen-

anthrenyl)porphyrin (9) (40 mg, 0.048 mmol), (thiophen-3-yl)-

boronic acid (62 mg, 0.48 mmol), Pd(PPh₃)₄(5.5 mg, 0.0048 mmol),

and K₃PO₄(206 mg, 0.974 mmol) in THF (30 mL) gave 18 mg

(0.021 mmol, 45%) of a purple solid after recrystallization from

CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.6 (CH₂Cl₂/n-hexane = 1:1,

5,15-Bis(4-methoxycarbonylphenyl)-10,20-bis(9-phenanthrenyl)-

porphyrin (21): Following general procedure C, 5,15-dibromo-

10,20-bis(9-phenanthrenyl)porphyrin (9) (40 mg, 0.048 mmol), (4-

1

v/v). H NMR (400 MHz, CDCl₃): δ = –2.38 (s, 2 H, NH), 7.19–

3

7.23 (m, 4 H, Ar-H), 7.69 (t, J = 7.8 Hz, 4 H, Ar-H), 7.84 (t, J

methoxycarbonylphenyl)boronic

acid

(87 mg,

0.48 mmol),

3

= 7.5 Hz, 2 H, Ar-H), 7.92 (t, J = 7.3 Hz, 2 H, Ar-H), 8.00 (d, J

Pd(PPh₃)₄(5.5 mg, 0.0048 mmol), and K₃PO₄(206 mg,

0.974 mmol) in THF (30 mL) gave 25 mg (0.026 mmol, 56%) of

a purple solid after recrystallization from CH₂Cl₂/CH₃OH; m.p.

Ͼ300 °C; R_f= 0.2 (CH₂Cl₂/n-hexane = 1:1, v/v). ¹H NMR

(400 MHz, CDCl₃): δ = –2.42 (s, 2 H, NH), 4.01 (s, 6 H, COOCH₃),

3

= 7.3 Hz, 2 H, Ar-H), 8.12 (d, J = 7.8 Hz, 2 H, Ar-H), 8.59 (t, J

3

= 7.8 Hz, 4 H, Ar-H), 8.75 (d, J = 4.5 Hz, 4 H, H_β), 8.90 (d, J =

4.5 Hz, 4 H, H_β), 9.05 (t, J = 8.3 Hz, 4 H, Ar-H) ppm. ¹³C NMR

3

(150 MHz, CDCl₃): δ = 13.69, 22.21, 31.14, 114.27, 117.17, 122.09,

122.42, 123.10, 125.89, 126.25, 126.95, 127.87, 128.67, 129.55,

130.44, 133.15, 133.96, 135.86, 137.38, 141.46 ppm. UV/Vis

(CH₂Cl₂): λ_max(logε) = 424 (5.28), 517 (4.03), 552 (3.58), 592

(3.51), 650 nm (3.22). HRMS (MS ES⁺) m/z calcd. for

[C₅₆H₃₅N₄S₂] [M + H⁺]: 827.2303; found 827.2288.

3

7.20 (m, 4 H, Ar-H), 7.72 (d, J = 8.2 Hz, 2 H, Ar-H), 7.84 (t, J

3

= 7, 2 H, 7.6 Hz, Ar-H), 7.94 (t, J = 7, 2 H, 8.2 Hz, Ar-H), 8.12

3

(d, J = 8.2 Hz, 2 H, Ar-H), 8.16 (d, J = 8.2 Hz, 2 H, Ar-H), 8.31

(m, 3 H, Ar-H), 8.43 (m, 3 H, Ar-H), 8.60 (d, ³J = 8.2 Hz, 2 H,

3

Ar-H), 8.73 (d, J = 4.7 Hz, 4 H, H_β), 8.77 (d, J = 4.1 Hz, 4 H,

H_β), 9.05 (t, J = 8.2 Hz, 4 H, Ar-H) ppm. ¹³C NMR (150 MHz,

3

5,15-Bis(9-phenanthrenyl)-10,20-bis(2-phenylethenyl)porphyrin (25):

Following general procedure C, 5,15-dibromo-10,20-bis(9-phen-

anthrenyl)porphyrin (9) (40 mg, 0.048 mmol), trans-β-styrylboronic

acid (71 mg, 0.48 mmol), Pd(PPh₃)₄(5.5 mg, 0.0048 mmol), and

K₃PO₄(203 mg, 0.96 mmol) in THF (30 mL) gave 22 mg

(0.025 mmol, 40%) of a purple solid after recrystallization from

CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.5 (CH₂Cl₂/n-hexane = 1:1,

v/v). ¹H NMR (400 MHz, CDCl₃): δ = –1.87 (s, 2 H, NH), 7.23

CDCl₃): δ = 51.96, 117.58, 118.56, 122.13, 122.42, 125.95, 126.30,

126.93, 127.00, 128.66, 129.76, 133.23, 134.01, 135.82, 137.14,

143.89, 146.16, 166.36, 166.79 ppm. UV/Vis (CH₂Cl₂): λ_max(logε)

= 424 (5.18), 516 (4.08), 549 (3.77), 592 (3.75), 645 nm (3.62).

HRMS: m/z calcd. for [C₆₄H₄₂N₄O₄]: 906.3207; found 906.3189.

5,15-Bis(4-cyanophenyl)-10,20-bis(9-phenanthrenyl)porphyrin (22):

Following general procedure C, 5,15-dibromo-10,20-bis(9-phen-

anthrenyl)porphyrin (9) (50 mg, 0.0611 mmol), (4-cyanophen-

yl)boronic acid (112 mg, 0.763 mmol), Pd(PPh₃)₄(7 mg,

0.00611 mmol), and K₃PO₄(325 mg, 1.53 mmol) in THF (30 mL)

gave 26 mg (0.030 mmol, 62%) of a purple solid after recrystalli-

zation from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.6 (CH₂Cl₂/n-

hexane = 1:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.46 (s, 2

H, NH), 7.14–7.20 (m, 4 H, Ar-H), 7.70 (t, ³J = 8.2, 2 H, 7 Hz,

3

(m, 4 H, Ar-H), 7.39 (d, J = 15.8 Hz, 2 H, alkene-H), 7.44 (t, J

3

= 7, 2 H, 7.6 Hz, Ar-H), 7.56 (t, J = 7.6, 4 H, 8.2 Hz, Ar-H), 7.70

3

(m, 2 H, Ar-H), 7.85 (t, J = 7.6, 2 H, 7 Hz, Ar-H), 7.91 (d, J =

3

7.6 Hz, 4 H, Ar-H), 7.96 (d, J = 7 Hz, 2 H, Ar-H), 8.15 (d, J =

7.6 Hz, 2 H, Ar-H), 8.61 (d, J = 11.1 Hz, 2 H, Ar-H), 8.75 (d, J

3

= 4.7 Hz, 4 H, H_β), 9.06 (t, J = 8.8 Hz, 4 H, Ar-H), 9.52 (d, J =

4.7 Hz, 4 H, H_β), 9.57 (d, J = 15.8 Hz, 2 H, alkene-H) ppm. ¹³C

3

NMR (150 MHz, CDCl₃): δ = 122.12, 122.43, 125.92, 126.27,

126.95, 127.88, 128.12, 128.57, 128.70, 129.52, 133.01, 142.80 ppm.

UV/Vis (CH₂Cl₂): λ_max(logε) = 439 (4.79), 582 (3.67), 672 nm

(3.38). HRMS (MS ES⁺) m/z calcd. for [C₆₄H₄₃N₄] [M + H⁺]:

867.3488; found 867.3465.

3

Ar-H), 7.85 (t, J = 7, 2 H, 7.6 Hz, Ar-H), 7.95 (t, J = 7 Hz, 2 H,

Ar-H), 8.05 (m, 4 H, Ar-H), 8.12 (d, ³J = 7.6 Hz, 2 H, Ar-H), 8.35

(d, J = 7.6 Hz, 4 H, Ar-H), 8.59 (d, J = 7.6 Hz, 2 H, Ar-H), 8.68

3

(d, J = 4.7 Hz, 4 H, H_β), 8.80 (d, J = 4.7 Hz, 4 H, H_β), 9.06 (t,

³J = 7.6, 4 H, 8.2 Hz, Ar-H) ppm. ¹³C NMR (150 MHz, CDCl₃):

δ = 30.26, 111.57, 117.52, 118.04, 122.21, 122.46, 126.02, 126.33, 5,15-Bis(4-methoxycarbonylphenyl)-10,20-bis(3-methoxyphenyl)por-

127.07, 128.65, 129.24, 129.42, 130.13, 130.35, 133.34, 134.42,

phyrin (26): Following general procedure C, 11 (50 mg,

135.78, 136.87, 146.20 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 424

0.073 mmol), (4-methoxycarbonylphenyl)boronic acid (164 mg,

5806

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Eur. J. Org. Chem. 2011, 5797–5816

Porphyrins for Use in Nonlinear Optics

3

0.91 mmol), Pd(PPh₃)₄(10.5 mg, 0.009 mmol), and K₃PO₄

(390 mg, 1.837 mmol) in THF (50 mL) were used. Purification by

column chromatography on silica gel (n-hexane/ethyl acetate =

10:1, v/v) followed by recrystallisation from CH₂Cl₂/CH₃OH af-

forded the title compound (45 mg, 0.056 mmol, 78%) as purple

6 H, OCH₃), 5.80 (br. s, 2 H, OH), 7.21 (d, J = 8.8 Hz, 4 H, Ar-

H), 7.36 (m, 2 H, Ar-H), 7.66 (t, ³J = 7.6 Hz, 2 H, Ar-H), 7.83 (m,

2 H, Ar-H), 8.08 (d, ³J = 9 Hz, 4 H, Ar-H), 8.90 (m, 8 H, H_β)

ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 53.2, 55.3, 113.4, 113.5,

119.5, 119.6, 120.3, 127.3, 127.5, 134.6, 135.5, 143.4, 155.3,

157.8 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 420 (5.03), 517 (4.72),

crystals; m.p. Ͼ 300 °C; R_f= 0.7 (n-hexane/ethyl acetate = 2:1, v/

v). H NMR (400 MHz, CDCl₃): δ = –2.77 (s, 2 H, NH), 4.02 (s, 552 (3.53), 593 (3.42), 647 nm (3.36). HRMS (MS ES⁺) m/z calcd.

1

6 H, OCH₃), 4.15 (s, 6 H, OCH₃), 7.37 (d, J = 8.2 Hz, 2 H, Ar- for [C₄₆H₃₅N₄O₄] [M + H⁺]: 707.2658; found 707.2658.

3

H), 7.68 (t, J = 7.6 Hz, 2 H, Ar-H), 7.83 (m, 4 H, Ar-H), 8.34 (d,

5,15-Bis(3-methoxyphenyl)-10,20-bis(2-phenylethenyl)porphyrin

(30): Following general procedure C, 11 (50 mg, 0.073 mmol),

3

³J = 7.6 Hz, 4 H, Ar-H), 8.48 (d, J = 8.2 Hz, 4 H, Ar-H), 8.83 (d,

3

³J = 4.7 Hz, 4 H, H_β3,7,13,17), 8.95 (d, J = 4.7 Hz, 4 H, H_β2,8,12,18

)

trans-β-styrylboronic acid (135 mg, 0.912 mmol), Pd(PPh₃)₄

(10.5 mg, 0.009 mmol), and K₃PO₄(389 mg, 1.837 mmol) in THF

(50 mL) were used. Purification by column chromatography on sil-

ica gel (n-hexane/CH₂Cl₂= 2:1, v/v) followed by recrystallization

from CH₂Cl₂/CH₃OH afforded the desired compound (25 mg,

0.0534 mmol, 47%) as purple crystals; m.p. Ͼ 300 °C; R_f= 0.62

(n-hexane/ethyl acetate = 6:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ

= –2.24 (s, 2 H, NH), 4.03 (s, 6 H, OCH₃), 7.38 (m, 2 H, Ar-H),

7.40 (d, ³J = 16.2 Hz, 2 H, CH=CH), 7.49 (m, 2 H, Ar-H), 7.61

(m, 4 H, Ar-H), 7.61 (m, 4 H, Ar-H), 7.69 (m, 2 H, Ar-H), 7.83

(m, 4 H, Ar-H), 7.97 (m, 4 H, Ar-H), 8.91 (d, ³J = 4.7 Hz, 4 H,

H_β), 9.47 (d, ³J = 4.7 Hz, 4 H, H_β), 9.64 (d, ³J = 16.4 Hz, 2 H,

CH=CH) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 29.5, 55.3, 113,

116.8, 120.1, 120.3, 126.8, 127.3, 127.4, 128.1, 128.7, 128.9, 37.8,

143.1, 143.4, 157.8 ppm. UV/Vis (CH₂Cl₂): λ_max(log ε) = 435

(4.94), 530 (3.43), 581 (3.78), 672 nm (3.42). HRMS (MS ES⁺) m/z

calcd. for [C₅₀H₃₉N₄O₂] [M + H⁺]: 727.3073; found 727.3087.

ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 52.4, 55.5, 113.6, 118.9,

120.3, 120.5, 127.5, 127.6, 127.9, 129.6, 134.5, 143.1, 146.9, 157.9,

167.3 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 419 (5.16), 516 (3.73),

550 (3.73), 594 (2.90), 646 nm (2.42). HRMS (MS ES⁺) m/z calcd.

for [C₅₀H₃₉N₄O₆] [M + H⁺]: 791.2870; found 791.2892.

5,15-Bis(4-cyanophenyl)-10,20-bis(3-methoxyphenyl)porphyrin (27):

Following general procedure C, 11 (50 mg, 0.073 mmol), (4-cya-

nophenyl)boronic acid (134 mg, 0.912 mmol), Pd(PPh₃)₄(10.5 mg,

0.009 mmol), and K₃PO₄(390 mg, 1.837 mmol) in THF (50 mL)

were used. Purification by column chromatography on silica gel

using n-hexane/ethyl acetate (6:1, v/v) followed by recrystallization

from CH₂Cl₂/CH₃OH gave the product (39 mg, 0.052 mmol, 73%)

as purple crystals; m.p. Ͼ 300 °C; R_f= 0.22 (n-hexane/ethyl acetate

1

= 6:1, v/v). H NMR (400 MHz, CDCl₃): δ = –2.81 (s, 2 H, NH),

3

4.02 (s, 6 H, OCH₃), 7.08 (d, J = 7.6 Hz, 2 H, Ar-H), 7.69 (t, J

3

= 8.2 Hz, 2 H, Ar-H), 7.81 (m, 4 H, Ar-H), 8.10 (d, J = 7.6 Hz, 4

3

5,15-Bis(1-methyl-1H-indol-5-yl)-10,20-bis(3-methoxyphenyl)-

porphyrin (31): Following general procedure C, 11 (50 mg,

0.073 mmol), (1-methylindol-5-yl)boronic acid pinacol ester

(235 mg, 0.912 mmol), Pd(PPh₃)₄(10.5 mg, 0.009 mmol), and

K₃PO₄(390 mg, 1.837 mmol) in THF (50 mL) were used. Purifica-

tion by column chromatography on silica gel (n-hexane/ethyl acet-

ate = 6:1, v/v) followed by recrystallisation from CH₂Cl₂/CH₃OH

afforded the title compound (38 mg, 0.048 mmol, 66%) as purple

crystals; m.p. Ͼ 300 °C; R_f= 0.42 (n-hexane/ethyl acetate = 6:1, v/

H, Ar-H), 8.36 (d, J = 8.2 Hz, 4 H, Ar-H), 8.76 (d, J = 4.7 Hz,

4 H, H_β3,7,13,17), 8.97 (d, ³J = 4.7 Hz, 4 H, H_β2,8,12,18) ppm. ¹³C

NMR (150 MHz, CDCl₃): δ = 55.3, 111.8, 113.5, 117.7, 118.8,

120.5, 120.6, 127.5, 130.4, 134.8, 142.8, 146.8, 157.9 ppm. UV/Vis

(CH₂Cl₂): λ_max(logε) = 420 (5.13), 515 (3.87), 550 (3.40), 591

(3.26), 645 nm (2.96). HRMS (MS ES⁺) m/z calcd. for

[C₄₈H₃₂N₆O₂] [M + H⁺]: 791.2870; found 791.2892.

5,15-Bis(3-methoxyphenyl)-10,20-bis(4-nitrophenyl)porphyrin (28):

Following general procedure C, 11 (50 mg, 0.073 mmol), (3-ni-

trophenyl)boronic acid (152 mg, 0.912 mmol), Pd(PPh₃)₄(10.5 mg,

0.009 mmol), and K₃PO₄(390 mg, 1.837 mmol) in THF (50 mL)

were used. Purification by column chromatography (silica gel, n-

hexane/CH₂Cl₂= 1:2, v/v) followed by recrystallization from

CH₂Cl₂/CH₃OH gave the desired compound (35 mg, 0.045 mmol,

63%) as purple crystals; m.p. Ͼ 300 °C; R_f= 0.42 (n-hexane/

1

v). H NMR (400 MHz, CDCl₃): δ = –2.63 (s, 2 H, NH), 4.00 (s,

3

6 H, OCH₃), 4.10 (s, 6 H, CH₃), 6.75 (d, J = 2.9 Hz, 2 H, Ar-H),

7.35 (m, 4 H, Ar-H), 7.66 (m, 4 H, Ar-H), 7.84 (m, 4 H, Ar-H),

3

8.14 (d, J = 8.2 Hz, 2 H, Ar-H), 8.47 (s, 2 H, Ar-H), 8.88 (dd, J

= 4.7 Hz, 8 H, H_β) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 33.0

55.3, 101.1, 106.7, 113.3, 119.3, 120.2, 121.2, 127.0, 127.5, 128.9,

133.2, 136.2, 143.6, 157.7 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 424

(4.94), 518 (3.52), 555 (3.22), 593 (3.06), 648 nm (3.06). HRMS

(MS ES⁺) m/z calcd. for [C₅₂H₄₁N₆O₂] [M + H⁺]: 781.3291; found

781.3284.

1

CH₂Cl₂= 1:2, v/v). H NMR (400 MHz, CDCl₃): δ = –2.79 (s, 2

H, NH), 3.99 (s, 6 H, OCH₃), 4.20 (s, 3 H, OCH₃), 7.38 (m, 2 H,

3

Ar-H), 7.68 (m, 2 H, Ar-H), 7.83 (m, 2 H, Ar-H), 7.99 (t, J = 7.6,

2 H, Hz, Ar-H), 8.58 (d, ³J = 7.6 Hz, 2 H, Ar-H), 8.72 (m, 2 H,

5,15-Bis(2-benzothiophenyl)-10,20-bis(3-methoxyphenyl)porphyrin

(32): Following general procedure C, 11 (50 mg, 0.073 mmol), (thia-

naphthalen-2-yl)boronic acid (152 mg, 0.91 mmol), Pd(PPh₃)₄

(10.5 mg, 0.009 mmol), and K₃PO₄(390 mg, 1.837 mmol) in THF

(50 mL) were used. Purification by filtration through a silica gel

column eluting with n-hexane/CH₂Cl₂(2:1, v/v) followed by

recrystallization from CH₂Cl₂/CH₃OH afforded purple crystals

(40 mg, 0.05 mmol, 70%); m.p. Ͼ 300 °C; R_f= 0.41 (n-hexane/ethyl

acetate = 6:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.65 (s, 2

H, NH), 4.01 (s, 6 H, OCH₃), 7.36 (m, 2 H, Ar-H), 7.6 (m, 6 H,

3

Ar-H), 8.76 (d, J = 4.7 Hz, 4 H, H_β3,7,13,17), 8.98 (d, J = 4.7 Hz,

4 H, H_β2,8,12,18), 10.11 (m, 2 H, Ar-H) ppm. ¹³C NMR (100 MHz,

CDCl₃): δ = 55.5, 77.2, 113.7, 120.4, 120.6, 123.0, 127.7, 128.3,

139.2 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 421 (5.16), 549 (3.88),

549 (3.29), 590 (3.25), 647 nm (2.48). HRMS (MS ES⁺) m/z calcd.

for [C₄₆H₃₃N₆O₆] [M + H⁺]: 765.2462; found 765.2428.

5,15-Bis(4-hydroxyphenyl)-10,20-bis(3-methoxyphenyl)porphyrin

(29): Following general procedure C, 11 (50 mg, 0.073 mmol), (4-

hydroxyphenyl)boronic acid (126 mg, 0.9125 mmol), Pd(PPh₃)₄

(10.5 mg, 0.009 mmol), and K₃PO₄(390 mg, 1.837 mmol) in THF

(50 mL) were used. Purification by two consecutive column chro-

matographies (1. n-hexane/ethyl acetate = 6:1, 2. n-hexane/ethyl

acetate = 2:1, v/v) and recrystallization from CH₂Cl₂/CH₃OH af-

forded the desired product (17 mg, 0.024 mmol, 32%) as purple

3

Ar-H), 7.8 (m, 4 H, Ar-H), 8.13 (t, J = 8.2 Hz, 4 H, Ar-H), 8.18

3

(s, 2 H, Ar-H), 8.92 (d, J = 4.7 Hz, 4 H, H_β3,7,13,17), 9.17 (d, J =

4.7 Hz, 4 H, H_β2,8,12,18) ppm. ¹³C NMR (100 MHz, CDCl₃): δ =

55.5, 113.7, 120.4, 121.7, 124.0, 124.9, 125.1, 127.6, 130.8,

143.0 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 425 (4.95), 518 (3.64),

556 (3.38), 593 (3.21), 648 nm (3.1). HRMS (MS ES⁺) m/z calcd.

crystals; m.p. Ͼ 300 °C; R_f= 0.37 (n-hexane/ethyl acetate = 2:1, v/

1

v). H NMR (400 MHz, CDCl₃): δ = –2.76 (s, 2 H, NH), 4.01 (s, for [C₅₀H₃₅N₄O₂S₂] [M + H⁺]: 787.2201; found 787.2178.

Eur. J. Org. Chem. 2011, 5797–5816

www.eurjoc.org

5807

M. O. Senge, M. Fazekas, M. Pintea, M. Zawadzka, W. J. Blau

column to give 150 mg (0.177 mmol, 90%) of a purple solid after

FULL PAPER

5,15-Bis(1-naphthyl)-10-(2-thianaphthyl)porphyrin (33): This com-

pound was obtained from the reaction described for 20 as 8 mg

recrystallization from CH₂Cl₂/MeOH. R_f= 0.36 (CH₂Cl₂/n-hexane

1

(0.011 mmol, 28 %) of purple solid after recrystallization from = 1:1, v/v). H NMR (400 MHz, CDCl₃): δ = 4.33 (s, 6 H, OCH₃),

3

CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.4 (CH₂Cl₂/n-hexane = 1:1,

6.99 (d, J = 8.8 Hz, 2 H, Ar-H), 7.13 (m, 2 H, Ar-H), 7.24 (m, 2

1

3

v/v). H NMR (400 MHz, CDCl₃): δ = –2.69 (s, 2 H, NH), 7.14–

H, Ar-H), 7.52 (t, ³J = 8.2, 2 H, 7 Hz, Ar-H), 8.15 (d, J = 7.6 Hz,

3

7.17 (m, 4 H, Ar-H), 7.55 (m, 2 H, Ar-H), 7.63 (m, 2 H, Ar-H),

2 H, Ar-H), 8.60 (d, J = 8.2 Hz, 2 H, Ar-H), 8.75 (d, J = 4.7 Hz,

3

7.92 (t, J = 7.8 Hz, 2 H, Ar-H), 8.09 (d, J = 8.8 Hz, 2 H, Ar-H),

4 H, H_β), 9.62 (d, J = 4.7 Hz, 4 H, H_β) ppm. UV/Vis (CH₂Cl₂):

3

8.16 (t, J = 7.8 Hz, 4 H, Ar-H), 8.20 (s, 2 H, Ar-H), 8.35 (d, J = λ_max(logε) = 430 (5.04), 559 (3.87), 598 nm (3.23). HRMS: m/z

3

7.8 Hz, 2 H, Ar-H), 8.67 (d, J = 4.9 Hz, 2 H, H_β), 8.74 (d, J =

4.9 Hz, 2 H, H_β), 9.09 (d, ³J = 4.9 Hz, 2 H, H_β), 9.27 (d, ³J =

4.9 Hz, 2 H, H_β), 10.24 (s, 1 H, H_meso) ppm. UV/Vis (CH₂Cl₂): λ_max

(logε) = 420 (4.71), 514 (3.57), 549 (3.22), 588 (3.25), 644 nm (3.08).

HRMS (MS ES⁺) m/z calcd. for [C₄₈H₃₁N₄S] [M + H⁺]: 695.2269;

found 695.2264.

calcd. for [C₄₂H₂₆N₄Br₂O₂Zn]: 839.9714; found 839.9747.

[5,15-Bis(1-naphthyl)-15,20-bis{(E)-2-(3-nitrophenyl)vinyl}por-

phyrinato]zinc(II) (39): Following general procedure F, 34 (50 mg,

0.063 mmol), 3-nitrostyrene (0.62 mL, 4.46 mmol), NaOAc (29 mg,

0.352 mmol), Pd(OAc)₂(1.4 mg, 0.0063 mmol), and PPh₃(6.6 mg,

0.0252 mmol) were added to a solution of DMF (50 mL) and

heated at 120 °C for 18 h. The crude product was purified by col-

umn chromatography using CH₂Cl₂with 10% n-hexane as eluent

to yield 23 mg (0.024 mmol, 40%) of a purple solid after recrystalli-

zation from CH₂Cl₂/n-hexane; m.p. Ͼ300 °C; R_f= 0.6 (CH₂Cl₂).

[5,15-Dibromo-10,20-bis(1-naphthyl)porphyrinato]zinc(II) (34): Fol-

lowing general procedure D, 10 (200 mg, 0.277 mmol) was dis-

solved in dry CH₂Cl₂(20 mL) and treated with a saturated solution

of zinc acetate dihydrate dissolved in CH₃OH. The reaction mix-

ture was stirred for 1 h and then washed with H₂O. The solvent

was removed under reduced pressure and the residue dissolved in

CH₂Cl₂and filtered through a short silica gel column to yield

200 mg (0.191 mmol, 92%) of a purple solid after recrystallization

from CH₂Cl₂/MeOH; m.p. Ͼ300 °C; R_f= 0.3 (CH₂Cl₂/n-hexane =

3

¹H NMR (400 MHz, CDCl₃): δ = 7.12 (m, 4 H, Ar-H), 7.41 (d, J

3

= 15.8 Hz, 2 H, alkene-H), 7.53 (m, 2 H, Ar-H), 7.74 (t, J = 7.6,

3

2 H, 8.2 Hz, Ar-H), 7.95 (t, J = 7, 2 H, 8.2 Hz, Ar-H), 8.20 (t, J

3

= 7.6 Hz, 4 H, Ar-H), 8.30 (t, J = 5.3, 2 H, 9.9 Hz, Ar-H), 8.35

(t, ³J = 7.6, 4 H, 6.4 Hz, Ar-H), 8.76 (d, ³J = 4.7 Hz, 4 H, H_β),

1

3

1:1, v/v). H NMR (400 MHz, CDCl₃): δ = 7.04 (m, 2 H, Ar-H),

8.78 (s, 2 H, Ar-H), 9.48 (d, J = 3.5 Hz, 4 H, H_β), 9.80 (d, J =

16.4 Hz, 2 H, alkene-H) ppm. ¹³C NMR (150 MHz, CDCl₃): δ =

116.54, 119.34, 121.09, 122.39, 124.11, 125.52, 126.01, 127.79,

128.51, 129.79, 130.06, 132.36, 136.67, 139.31, 139.68, 148.88,

149.36, 150.45 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 439 (4.96),

565 (3.82), 615 nm (3.85). C₅₆H₃₄N₆O₄Zn (920.30): calcd. C 73.09,

H 3.72, N 9.13; found C 73.28, H 3.66, N 9.27.

3

7.12 (m, 2 H, Ar-H), 7.53 (t, J = 7, 2 H, 8.2 Hz, Ar-H), 7.92 (t,

³J = 7, 2 H, 7.6 Hz, Ar-H), 8.19 (d, J = 8.2 Hz, 2 H, Ar-H), 8.26

3

(d, J = 6.4 Hz, 2 H, Ar-H), 8.35 (d, J = 8.2 Hz, 2 H, Ar-H), 8.69

(d, ³J = 4.7 Hz, 4 H, H_β), 9.62 (d, J = 4.7 Hz, 4 H, H_β) ppm. UV/

3

Vis (CH₂Cl₂): λ_max(logε) = 428 (4.99), 558 (3.74), 598 nm (3.48).

C₄₀H₂₂N₄Br₂Zn (783.83): calcd. C 61.29, H 2.83, N 7.15; found C

61.55, H 3.05, N 7.43.

[5,15-Bis{(E)-2-(4-bromophenyl)vinyl}-10,20-bis(1-naphthyl)por-

phyrinato]zinc(II) (40): Following general procedure F, 34 (50 mg,

0.063 mmol), 3-nitrostyrene (0.62 mL, 4.46 mmol), NaOAc (29 mg,

0.352 mmol), Pd(OAc)₂(1.4 mg, 0.0063 mmol), and PPh₃(6.6 mg,

0.0252 mmol) were added to a solution of DMF (50 mL) and

heated at 120 °C for 18 h. The crude product was purified by col-

umn chromatography using CH₂Cl₂with 10% n-hexane as eluent

to yield 24 mg (0.023 mmol, 38%) of a purple solid after recrystalli-

zation from CH₂Cl₂/n-hexane; m.p. Ͼ300 °C; R_f= 0.6 (CH₂Cl₂).

¹H NMR (400 MHz, CDCl₃): δ = 7.09–7.13 (m, 4 H, Ar-H), 7.29

(d, ³J = 15.8 Hz, 2 H, alkene-H), 7.53 (d, ³J = 8.2 Hz, 2 H, Ar-H),

7.68 (d, ³J = 8.7 Hz, 4 H, Ar-H), 7.78 (d, ³J = 8.7 Hz, 4 H, Ar-H),

[5,15-Bis(4-cyanophenyl)-10,20-bis(1-naphthyl)porphyrinato]-

zinc(II) (36): Following general procedure E, 14 (40 mg,

0.052 mmol) was treated with zinc oxide (400 mg) to yield 38 mg

(0.009 mmol, 68%) of desired the product after recrystallization

from CH₂Cl₂/MeOH; m.p. Ͼ300 °C; R_f= 0.6 (CH₂Cl₂/n-hexane =

1:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = 7.09–7.13 (m, 4 H, Ar-

3

H), 7.53 (m, 2 H, Ar-H), 7.92 (t, J = 7.6 Hz, 2 H, Ar-H), 8.04 (d,

³J = 8.8 Hz, 4 H, Ar-H), 8.19 (d, ³J = 8.2 Hz, 2 H, Ar-H), 8.34

(m, 8 H, Ar-H), 8.76 (m, 8 H, H_β) ppm. UV/Vis (CH₂Cl₂): λ_max

(log ε) = 429 (5.19), 560 (3.99), 601 nm (3.45). C₅₄H₃₀N₆Zn

(828.25): calcd. C 78.31, H 3.65, N 10.15; found C 78.05, H 3.74,

N 9.87.

3

7.93 (t, J = 8.7 Hz, 2 H, Ar-H), 8.19 (d, J = 8.2 Hz, 2 H, Ar-H),

3

8.34 (t, J = 8.2 Hz, 4 H, Ar-H), 8.72 (d, J = 4.7 Hz, 4 H, H_β),

[5,15-Bis(1-naphthyl)-10,20-bis(4-nitrophenyl)porphyrinato]zinc(II)

(37): Following general procedure E, 15 (20 mg, 0.024 mmol) was

treated with zinc oxide (300 mg) to give 15 mg (0.0170 mmol, 70%)

of the desired product after recrystallization from CH₂Cl₂/MeOH;

m.p. Ͼ300 °C; R_f= 0.5 (CH₂Cl₂/n-hexane = 1:1, v/v). ¹H NMR

(400 MHz, CDCl₃): δ = 7.06–7.14 (m, 4 H, Ar-H), 7.52 (t, ³J =

3

9.47 (d, J = 4.7 Hz, 4 H, H_β), 9.67 (d, J = 15.8 Hz, 2 H, alkene-

H) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 117.32, 119.02, 121.83,

124.10, 125.49, 125.97, 127.76, 128.15, 128.47, 130.15, 131.98,

132.10, 132.34, 132.77, 136.74, 139.74, 141.10, 149.49, 150.30 ppm.

UV/Vis (CH₂Cl₂): λ_max(log ε) = 441 (5.13), 567 (3.86), 601 nm

(3.94). C₅₆H₃₄Br₂N₄Zn (988.10): calcd. C 68.07, H 3.47, N 5.67;

found C 67.84, H 3.72, N 5.51.

3

8.2 Hz, 2 H, Ar-H), 7.92 (t, J = 7, 2 H, 8.2 Hz, Ar-H), 8.19 (d, J

3

= 8.2 Hz, 2 H, Ar-H), 8.31 (m, 2 H, Ar-H), 8.35 (d, J = 8.2 Hz, 2

3

H, Ar-H), 8.41 (dd, J = 7 Hz, 4 H, Ar-H), 8.62 (m, 4 H, Ar-H),

[5,15-Bis[(E)-2-methoxycarbonylethenyl]-10,20-bis(1-naphthyl)por-

phyrinato]zinc(II) (41): Following general procedure F, 34 (50 mg,

0.063 mmol), methyl acrylate (0.4 mL, 4.46 mmol), NaOAc (29 mg,

0.352 mmol), Pd(OAc)₂(1.4 mg, 0.0063 mmol), and PPh₃(6.6 mg,

8.77 (dd, ³J = 4.7 Hz, 8 H, H_β) ppm. UV/Vis (CH₂Cl₂): λ_max(logε)

= 431 (4.98), 561 (3.78), 606 nm (3.27). C₅₂H₃₀N₆O₄Zn (868.23):

calcd. C 71.94, H 3.48, N 9.68; found C 72.15, H 3.54, N 9.78.

[5,15-Dibromo-10,20-bis(4-methoxy-1-naphthyl)porphyrinato]- 0.0252 mmol) were added to a solution of DMF (50 mL) and

zinc(II) (38): Following general procedure D, 12 (150 mg,

0.192 mmol) was dissolved in dry CH₂Cl₂(30 mL) and treated with

a saturated solution of zinc acetate dihydrate solved in CH₃OH.

The reaction mixture was stirred for 1 h and then washed with

H₂O. The solvent was removed under reduced pressure and the

residues dissolved in CH₂Cl₂and filtered through a short silica gel

heated at 120 °C for 18 h. The crude product was purified by col-

umn chromatography using CH₂Cl₂with 10% n-hexane as eluent

to give 15 mg (0.018 mmol, 30%) of a purple solid after recrystalli-

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

3

¹H NMR (400 MHz, CDCl₃): δ = 1.27 (s, 6 H, CH₃), 6.66 (d, J =

15.8 Hz, 2 H, alkene-H), 7.04 (d, ³J = 8.2 Hz, 2 H, Ar-H), 7.11 (d,

5808

www.eurjoc.org

Eur. J. Org. Chem. 2011, 5797–5816

Porphyrins for Use in Nonlinear Optics

³J = 7, 2 H, 8.8 Hz, Ar-H), 7.53 (t, ³J = 7, 2 H, 8.2 Hz, Ar-H),

(40 mg, 0.0538 mmol), methyl acrylate (0.33 mL, 3.76 mmol),

NaOAc (24.7 mg, 0.3 mmol), Pd(OAc)₂(1.2 mg, 0.00538 mmol),

3

7.94 (t, J = 8.2 Hz, 2 H, Ar-H), 8.20 (d, J = 8.2 Hz, 2 H, Ar-H),

3

8.36 (m, 4 H, Ar-H), 8.74 (d, J = 4.7 Hz, 4 H, H_β), 9.42 (d, J = and PPh₃(5.6 mg, 0.0215 mmol) in DMF (50 mL) were used. Puri-

5.3 Hz, 4 H, H_β), 10.16 (d, ³J = 15.8 Hz, 2 H, alkene-H) ppm. UV/

Vis (CH₂Cl₂): λ_max(logε) = 435 (4.93), 565 (3.76), 611 nm (3.70).

C₄₈H₃₂N₄O₄Zn (794.19): calcd. C 72.59, H 4.06, N 7.05; found C

72.66, H 3.89, N 7.21.

fication by column chromatography on silica gel (n-hexane/ethyl

acetate = 2:1, v/v) gave a purple solid (20 mg, 0.026 mmol, 49%);

m.p. Ͼ 300 °C; R_f= 0.33 (n-hexane/ethyl acetate = 6:1, v/v). ¹H

NMR (400 MHz, CDCl₃): δ = 3.73 (s, 6 H, OCH₃), 3.89 (s, 6 H,

OCH₃), 6.39 (d, ³J = 15.7 Hz, 2 H, CH=CH), 7.28 (m, 2 H, Ar-

H), 7.61 (m, 2 H, Ar-H), 7.73 (m, 2 H, Ar-H), 8.92 (d, ³J = 4.7 Hz,

4 H, H_β), 9.08 (d, J = 4.9 Hz, 4 H, H_β), 9.91 (d, J = 15.7 Hz, 2

H, CH=CH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 13.6, 22.2,

28.9, 31.1, 50.2, 51.4, 55.0, 112.9, 113.7, 120.0, 121.7, 127.0, 129.4,

132.4, 143.2, 146.3, 148.5, 157.4, 166.1 ppm. UV/Vis (CH₂Cl₂):

λ_max(logε) = 433 (4.98), 564 (3.71), 613 nm (3.76).

[5,15-Bis[(E)-2-ethoxycarbonylethenyl]-10,20-bis(1-naphthyl)por-

phyrinato]zinc(II) (42): Following general procedure F, 34 (50 mg,

0.063 mmol), ethyl acrylate (0.5 mL, 4.46 mmol), NaOAc (29 mg,

0.352 mmol), Pd(OAc)₂(1.4 mg, 0.0063 mmol), and PPh₃(6.6 mg,

0.0252 mmol) were added to a solution of DMF (50 mL) and

heated at 120 °C for 18 h. The crude product was purified by col-

umn chromatography (ethyl acetate) to yield 20 mg (0.023 mmol,

40%) of purple solid after recrystallization from CH₂Cl₂/n-hexane;

3

[5,15-Bis[(E)-2-ethoxycarbonylethenyl]-10,20-bis(3-methoxy)-

phenyl)porphyrinato]zinc(II) (46): Following general procedure F, 35

(40 mg, 0.0538 mmol), ethyl acrylate (0.4 mL, 3.76 mmol), NaOAc

(24.7 mg, 0.3 mmol), Pd(OAc)₂(1.2 mg, 0.00538 mmol), and PPh₃

(5.6 mg, 0.0215 mmol) in DMF (50 mL) were used. Purification by

column chromatography on silica gel (n-hexane/ethyl acetate = 2:1,

v/v) followed by recrystallization from CH₂Cl₂/n-hexane afforded

the desired product (35 mg, 0.044 mmol, 83%) as purple crystals;

m.p. Ͼ 300 °C; R_f= 0.35 (n-hexane/ethyl acetate = 6:1, v/v). ¹H

1

m.p. Ͼ300 °C; R_f= 0.2 (CH₂Cl₂). H NMR (400 MHz, CDCl₃): δ

= 1.30 (t, ³J = 6.4 Hz, 6 H, CH₂CH₃), 4.07 (m, 4 H, CH₂CH₃),

6.23 (d, ³J = 15.2 Hz, 2 H, alkene-H), 7.09 (m, 4 H, Ar-H), 7.52

3

(d, J = 6.4 Hz, 2 H, 7, Ar-H), 7.93 (t, J = 7, 2 H, 8.2 Hz, Ar-H),

3

8.21 (d, J = 8.2 Hz, 2 H, Ar-H), 8.34 (m, 4 H, Ar-H), 8.69 (d, J

3

= 4.7 Hz, 4 H, H_β), 9.27 (d, J = 4.1 Hz, 4 H, H_β), 9.83 (d, J =

15.7 Hz, 2 H, alkene-H) ppm. ¹³C NMR (150 MHz, CDCl₃): δ =

13.80, 60.29, 113.81, 119.58, 123.79, 124.26, 125.24, 125.73, 126.17,

127.49, 128.07, 128.24, 129.67, 130.01, 132.31, 136.33, 139.17,

145.86, 148.63, 150.37, 150.87 ppm. UV/Vis (CH₂Cl₂): λ_max(logε)

= 435 (4.92), 566 (3.66), 613 nm (3.63). C₅₀H₃₆N₄O₄Zn (822.24):

calcd. C 73.04, H 4.41, N 6.81; found C 73.28, H 4.26, N 6.66.

3

NMR (400 MHz, CDCl₃): δ = 1.32 (t, J = 7 Hz, 6 H, CH₂CH₃),

3.93 (s, 6 H, OCH₃), 4.07 (m, 4 H, CH₂CH₃), 6.22 (d, ³J = 15.2 Hz,

2 H, CH=CH), 7.34 (d, ³J = 8.2 Hz, 2 H, Ar-H), 7.69 (m, 4 H, Ar-

3

H), 7.82 (d, J = 7 Hz, 2 H, Ar-H), 9.00 (d, J = 4.7 Hz, 4 H, H_β),

9.34 (d, ³J = 4.7 Hz, 4 H, H_β), 9.80 (d, ³J = 15.2 Hz, 2 H, CH=CH)

ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 55.0, 60.2, 112.9, 113.7,

120.1, 121.7, 127.0, 127.1, 129.4, 129.9, 132.3, 143.2, 145.9, 148.5,

149.6, 157.3, 165.6 ppm. UV/Vis (CH₂Cl₂): λ_max(log ε) = 433

(4.96), 564 (3.38), 611 nm (3.44).

[5,15-Bis[(E)-diethylprop-1-enyl phosphonate]-10,20-bis(1-naphthyl)-

porphyrinato]zinc(II) (43): Following general procedure F, 34

(50 mg, 0.063 mmol), diethyl vinylphosphonate (0.6 mL,

4.46 mmol), NaOAc (29 mg, 0.352 mmol), Pd(OAc)₂(1.4 mg,

0.0063 mmol), and PPh₃(6.6 mg, 0.0252 mmol) were added to a

solution of DMF (50 mL) and heated at 120 °C for 18 h. The crude

product was purified by column chromatography using ethyl acet-

ate/n-hexane = 4:1 (v/v) as eluent to yield 23 mg (0.023 mmol, 58%)

of a purple solid after recrystallization from CH₂Cl₂/n-hexane; m.p.

Ͼ300 °C; R_f= 0.23 (ethyl acetate/n-hexane = 4:1, v/v). ¹H NMR

(400 MHz, CDCl₃): δ = 0.95 (s, 12 H, OCH₂CH₃), 3.28 (m, 8 H,

OCH₂CH₃), 5.31 (br., 2 H, alkene-H), 7.14 (m, 2 H, Ar-H), 7.19

[5,15-Bis[(E)-diethylprop-1-enyl phosphonate)-10,20-bis(3-meth-

oxyphenyl)porphyrinato]zinc(II) (47): Following general procedure

F, 35 (40 mg, 0.0538 mmol), diethyl vinylposphonate (0.58 mL,

3.76 mmol), NaOAc (24.7 mg, 0.3 mmol), Pd(OAc)₂(1.2 mg,

0.00538 mmol), and PPh₃(5.6 mg, 0.0215 mmol) in DMF (50 mL)

were used. Recrystallization from CH₂Cl₂/n-hexane afforded the

desired product (37 mg, 0.040 mmol, 75%) as purple crystals; m.p.

3

(m, 2 H, Ar-H), 7.51 (t, J = 7, 2 H, 7.6 Hz, Ar-H), 7.95 (t, J =

1

Ͼ 300 °C; R_f= 0.35 (n-hexane/ethyl acetate = 2:1, v/v). H NMR

3

7.6 Hz, 2 H, Ar-H), 8.21 (d, J = 8.2 Hz, 2 H, Ar-H), 8.36 (t, J =

8.2 Hz, 4 H, Ar-H), 8.60 (d, J = 4.7 Hz, 4 H, H_β), 8.79 (br., 6 H,

(400 MHz, CDCl₃): δ = 0.93 (br. s, 12 H, OCH₂CH₃), 3.21 (br. s,

8 H, OCH₂CH₃), 4.09 (s, 6 H, OCH₃), 5.21 (br. s, 2 H, CH=CH),

3

overlapping alkene-H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ =

15.84, 61.39, 124.02, 125.44, 125.78, 127.73, 128.26, 128.64, 129.30,

132.22, 132.75, 136.96, 140.31, 148.39, 150.74 ppm. UV/Vis

(CH₂Cl₂): λ_max(logε) = 433 (4.98), 568 (3.89), 614 nm (3.80).

3

7.44 (m, 2 H Ar-H), 7.77 (t, J = 7.8 Hz, 2 H, Ar-H), 7.91 (m, 4

H, Ar-H), 8.59 (br. s, 2 H, CH=CH), 8.87 (br. s, 4 H, H_β), 9.01 (d,

³J = 4.7 Hz, 4 H, H_β) ppm. ¹³C NMR (100 MHz, CDCl₃): δ =

15.6, 55.1, 61.1, 112.5, 113.8, 120.5, 113.8, 120.5, 123.4, 125.2,

126.9, 127.4, 131.9, 144.4, 148.0, 149.9, 150.0, 157.4 ppm. UV/Vis

(CH₂Cl₂): λ_max(log ε) = 430 (5.01), 569 (3.64), 630 nm (4.65).

HRMS (MS ES⁺) m/z calcd. for [C₄₆H₄₇N₄O₈P₂Zn] [M + H⁺]:

909.2161; found 909.2202.

[5,15-Bis(3-methoxyphenyl)-10,20-bis{(E)-2-(3-nitrophenyl)-

vinyl}porphyrinato]zinc(II) (44): Following general procedure F, 35

(40 mg, 0.0538 mmol), 3-nitrostyrene (0.52 mL, 3.76 mmol),

NaOAc, (24.7 mg, 0.3 mmol), Pd(OAc)₂(1.2 mg, 0.00538 mmol),

and PPh₃(5.6 mg, 0.0215 mmol) in DMF (50 mL) were used. Puri-

fication by column chromatography on silica gel (n-hexane/ethyl

acetate = 2:1, v/v) afforded purple crystals (20 mg, 0.022 mmol,

42%); m.p. Ͼ 300 °C; R_f= 0.33 (n-hexane/ethyl acetate = 6:1, v/v).

¹H NMR (400 MHz, CDCl₃): δ = 3.93 (s, 6 H, OCH₃), 7.29 overlap

(m, ³J = 15.7 Hz, 2 H, Ar-H, d, 2 H, CH=CH), 7.58–7.73 (m, 8

5,15-Bis(1-naphthyl)-5,15-bis(phenylethynyl)porphyrin (48): Follow-

ing general procedure G, 10 (50 mg, 0.069 mmol), phenylacetylene

(0.17 mL, 0.152 mmol), CuI (3.3 mg, 0.01725 mmol), and Pd)-

(PPh₃)₂Cl₂(4.8 mg, 0.0069 mmol) were added to a mixture of THF

(5 mL) and triethylamine (15 mL). After 10 min, the cold bath was

removed and the reaction mixture was stirred for 3 h at room temp.

The crude product was purified by flash column chromatography

eluting with CH₂Cl₂/n-hexane = 1:3 (v/v) to give 23 mg

(0.030 mmol, 43%) of a purple solid after recrystallization from

CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.6 (CH₂Cl₂/n-hexane = 1:1,

3

H, Ar-H), 8.11 (d, J = 8.3 Hz, 2 H, Ar-H), 8.71 (s, 2 H, Ar-H),

3

8.92 (d, ³J = 4.4 Hz, 4 H, H_β), 9.41 (d, J = 4.4 Hz, 4 H, H_β), 9.68

(d, ³J = 15.7 Hz, 2 H, CH=CH) ppm. UV/Vis (CH₂Cl₂): λ_max(logε)

= 437 (5.00), 565 (3.75), 615 nm (3.84).

[5,15-Bis[(E)-2-methoxycarbonylethenyl]-10,20-bis(3-methoxy)- v/v). ¹H NMR (400 MHz, CDCl₃): δ = –1.68 (s, 2 H, NH), 7.18

phenylporphyrinato]zinc(II) (45): Following general procedure F, 35

3

(m, 4 H, Ar-H), 7.50 (d, J = 7.6 Hz, 2 H, Ar-H), 7.56 (t, J = 6.4,

Eur. J. Org. Chem. 2011, 5797–5816

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5809

M. O. Senge, M. Fazekas, M. Pintea, M. Zawadzka, W. J. Blau

FULL PAPER

3

6 H, 7.6 Hz, Ar-H), 7.94 (t, J = 8.2, 2 H, 7 Hz, Ar-H), 8.00 (t, J 0.60 [s, 18 H, SiC(CH₃)₃], 7.08 (m, 4 H, Ar-H), 7.53 (t, J = 8.2, 2

3

= 7 Hz, 4 H, Ar-H), 8.20 (d, J = 8.2 Hz, 2 H, Ar-H), 8.31 (t, J

H, 6.4 Hz, Ar-H), 7.93 (t, J = 8.2, 2 H, 7 Hz, Ar-H), 8.19 (d, J

3

= 7, 2 H, 8.8 Hz, Ar-H), 8.36 (d, J = 8.2 Hz, 2 H, Ar-H), 8.60 (d, = 8.2 Hz, 2 H, Ar-H), 8.29 (t, J = 6.4 Hz, 2 H, Ar-H), 8.34 (d, J

³J = 4.1 Hz, 4 H, H_β), 9.61 (d, ³J = 4.7 Hz, 4 H, H_β) ppm. ¹³C = 8.2 Hz, 2 H, Ar-H), 8.67 (d, J = 4. 7 Hz, 4 H, H_β), 9.62 (d, J

NMR (150 MHz, CDCl₃): δ = 91.16, 96.85, 100.79 119.03, 123.29, = 4.7 Hz, 4 H, H_β) ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 448 (5.04),

123.88, 125.38, 125.94, 127.46, 128.48, 132.18, 132.49, 136.18, 577 (3.70), 636 nm (4.15). HRMS: m/z calcd. for [C₅₀H₄₀N₄Si₂Zn]:

3

138.06 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 445 (5.16), 598 (4.25),

689 nm (3.83). HRMS (MS ES⁺) m/z calcd. for [C₅₆H₃₅N₄] [M +

H⁺]: 763.2862; found 763.2887.

calcd. 816.2083; found 816.2068.

[5,15-Diethynyl-10,20-bis(1-naphthyl)porphyrinato]zinc(II) (52):

TBAF (0.1 mL of a 1 m solution in THF) was added to a solution

of 51 (20 mg, 0.024 mmol) in CH₂Cl₂(20 mL). The reaction mix-

ture was stirred for 20 min, and the crude product was filtered

through a short silica gel column and purified by recrystallization

from CH₂Cl₂/CH₃OH to give 16 mg (0.023 mmol, 94%) of a purple

solid; m.p. Ͼ300 °C; R_f= 0.4 (CH₂Cl₂/n-hexane = 2:1, v/v). ¹H

NMR (400 MHz, CDCl₃): δ = 4.09 (s, 2 H, CϵCH), 7.13 (m, 4 H,

[5,15-Bis(1-naphthyl)-10,20-bis(phenylethynyl)porphyrinato]zinc(II)

(49): Following general procedure G, 34 (50 mg, 0.063 mmol),

phenylacetylene (0.15 mL, 0.140 mmol), CuI (3 mg, 0.016 mmol),

and Pd(PPh₃)₂Cl₂(4.4 mg, 0.0063 mmol) were added to a mixture

of THF (5 mL) and triethylamine (15 mL). The cold bath was re-

moved after 10 min and the reaction mixture was stirred for 24 h

at room temp. The crude product was purified by flash column

chromatography eluting with CH₂Cl₂/n-hexane = 1:2 (v/v) to yield

32 mg (0.038 mmol, 60%) of a purple solid after recrystallization

from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.5 (CH₂Cl₂/n-hexane

= 1:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = 7.05 (m, 2 H, Ar-H),

3

Ar-H), 7.43 (d, J = 7.6 Hz, 2 H, Ar-H), 7.54 (t, J = 7 Hz, 2 H,

3

Ar-H), 7.83 (t, J = 7 Hz, 2 H, Ar-H), 8.20 (d, J = 8.2 Hz, 2 H,

Ar-H), 8.35 (d, ³J = 8.2 Hz, 2 H, Ar-H), 8.70 (d, J = 4.1 Hz, 4 H,

3

H_β), 9.62 (d, J = 4.7 Hz, 4 H, H_β) ppm. UV/Vis (CH₂Cl₂): λ_max

(log ε) = 432 (4.99), 568 (3.65), 609 nm (3.66). C₄₄H₂₄N₄Zn

(674.08): calcd. C 78.40, H 3.59, N 8.32; found C 78.59, H 8.02, N

8.52.

3

7.13 (m, 4 H, Ar-H), 7.54 (t, J = 6.9 Hz, 5 H, Ar-H), 7.94 (m, 5

3

H, Ar-H), 8.20 (d, J = 7.8 Hz, 2 H, Ar-H), 8.29 (t, J = 6.9, 2 H,

8.8 Hz, Ar-H), 8.36 (d, ³J = 7.8 Hz, 2 H, Ar-H), 8.69 (m, 4 H, H_β),

9.62 (d, ³J = 4.9 Hz, 2 H, Ar-H), 9.69 (d, ³J = 4.9 Hz, 2 H, H_β)

ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 91.59, 96.13, 104.77,

119.66, 123.80, 125.28, 125.83, 127.48, 128.23, 131.02, 131.16,

132.18, 132.27, 132.69, 132.83, 133.01, 136.37, 138.81, 149.22,

149.86, 150.32, 151.08 ppm. 152.37. UV/Vis (CH₂Cl₂): λ_max(logε)

= 440 (4.70), 567 (3.52), 614 nm (3.54). HRMS (MS ES⁺) m/z

calcd. for [C₅₆H₃₃N₄Zn] [M + H⁺]: 827.2153; found 827.2155.

5,15-Bis(3-methoxyphenyl)-10,20-bis(phenylethynyl)porphyrin (53):

Following general procedure G, 11 (50 mg, 0.0734 mmol), phenyl-

acetylene (0.176 mL, 0.161 mmol), CuI (3.5 mg, 0.0146 mmol), and

Pd(PPh₃)₂Cl₂(5.2 mg, 0.00734 mmol) were added to triethylamine

(15 mL) and THF (5 mL). Purification by column chromatography

on silica gel (n-hexane/CH₂Cl₂= 4:1, v/v) gave purple crystals

(20 mg, 0.027 mmol, 38 %); m.p. Ͼ 300 °C; R_f= 0.6 (n-hexane/

1

CH₂Cl₂= 1:1, v/v). H NMR (400 MHz, CDCl₃): δ = –1.96 (s, 2

H, NH), 4.05 (s, 6 H, OCH₃), 7.40 (d, ³J = 8.2 Hz, 2 H, Ar-H),

7.53 (m, 4 H, Ar-H), 7.60 (m, 4 H, Ar-H), 7.71 (t, ³J = 8.2, 2

5,15-Bis(1-naphthyl)-10,20-bis(trimethylsilanylethynyl)porphyrin

(50): Following general procedure G, 10 (50 mg, 0.069 mmol), eth-

ynyltrimethylsilane (0.2 mL, 0.152 mmol), CuI (3.3 mg,

0.01725 mmol), and Pd(PPh₃)₂Cl₂(4.8 mg, 0.0069 mmol) were

added to a mixture of THF (5 mL) and triethylamine (15 mL). Af-

ter 10 min the cold bath was removed and the reaction mixture was

stirred for 3 h at room temp. The crude product was purified by

flash column chromatography eluted with CH₂Cl₂/n-hexane = 1:2

(v/v) to give 30 mg (0.040 mmol, 58 %) of a purple solid after

recrystallization from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.7

(CH₂Cl₂/n-hexane = 2:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ =

–1.91 (s, 2 H, NH), 0.57 [s, 18 H, SiC(CH₃)₃], 7.13 (m, 4 H, Ar-

3

H, Hz, Ar-H), 7.82 (m, 2 H, Ar-H), 8.05 (d, J = 7.6 Hz, 4 H, Ar-

3

H), 8.92 (d, J = 4.1 Hz, 4 H, H_β), 9.71 (d, J = 4.9 Hz, 4 H, H_β)

ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 52.9, 54.3, 55.8, 57.2, 91.4,

96.8, 100.7, 112.5, 114.1, 120.7, 121.1, 123.3, 126.2, 126.3, 127.4,

127.9, 128.0, 129.2, 130.4, 132.0, 142.1, 142.2, 157.6 ppm. UV/Vis

(CH₂Cl₂): λ_max(log ε) = 442 (4.94), 554 (3.33), 598 (4.06), 627

(3.22), 689 nm (3.76). HRMS (MS ES⁺) m/z calcd. for

[C₅₀H₃₅N₄O₂] [M + H⁺]: 723.2760; found 723.2783.

[5,15-Bis(3-methoxyphenyl)-10,20-bis(phenylethynyl)porphyrin-

ato])zinc(II) (54): Following general procedure G, 35 (40 mg,

0.053 mmol), phenylacetylene (2.5 mg, 0.01325 mmol), CuI

(3.7 mg, 0.0053 mmol), and Pd(PPh₃)₂Cl₂(3.7 mg, 0.0053 mmol)

were added to triethylamine (15 mL) and THF (5 mL). Purification

by column chromatography on silica gel (n-hexane/CH₂Cl₂= 2:1, v/

v) gave the desired compound (27 mg, 0.034 mmol, 65%) as purple

crystals; m.p. Ͼ 300 °C; R_f= 0.55 (n-hexane/CH₂Cl₂= 1:1, v/v).

¹H NMR (400 MHz, CDCl₃): δ = 4.03 (s, 6 H, OCH₃), 7.39 (m, 2

3

H), 7.54 (m, 2 H, Ar-H), 7.92 (t, J = 8.2, 2 H, 7 Hz, Ar-H), 8.19

3

(d, J = 8.2 Hz, 2 H, Ar-H), 8.27 (d, J = 6.4 Hz, 2 H, Ar-H), 8.35

3

(d, J = 8.2 Hz, 2 H, Ar-H), 8.58 (d, J = 4.7 Hz, 4 H, H_β), 9.52

3

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

0.58, 29.26, 100.43, 102.27, 106.07, 118.88, 123.85, 125.35, 125.91,

127.44, 128.46, 132.17, 132.48, 136.20, 138.01 ppm. UV/Vis

(CH₂Cl₂): λ_max(log ε) = 436 (4.86), 542 (3.51), 582 (3.91), 616

(3.19), 678 nm (3.45). HRMS (MS ES⁺) m/z calcd. for

[C₅₀H₄₃N₄Si₂] [M + H⁺]: 755.3026; found 755.3024.

3

H, Ar-H), 7.53 (d, J = 7.8 Hz, 2 H, Ar-H), 7.60 (t, J = 7.8 Hz, 4

H, Ar-H), 7.70 (t, ³J = 7.8 Hz, 2 H, Ar-H), 7.79 (s, 4 H, Ar-H),

7.83 (d, ³J = 7.8 Hz, 2 H, Ar-H), 8.04 (d, ³J = 6.9 Hz, 2 H, Ar-H),

[5,15-Bis(1-naphthyl)-10,20-bis(trimethylsilanylethynyl)porphyrin)-

ato]zinc(II) (51): Following general procedure G, 34 (40 mg,

0.051 mmol), ethynyltrimethylsilane (0.15 mL, 0.112 mmol), CuI

(2.5 mg, 0.01275 mmol), and Pd(PPh₃)₂Cl₂(3.5 mg, 0.0051 mmol)

were added to a mixture of THF (5 mL) and triethylamine (15 mL).

After 10 min, the cold bath was removed and the reaction mixture

was stirred for 3 h at room temp. The crude product was purified

by flash column chromatography eluting with CH₂Cl₂/n-hexane =

1:2 (v/v) to yield 20 mg (0.024 mmol, 48%) of a purple solid after

3

9.01 (d, J = 3.9 Hz, 4 H, H_β), 9.78 (d, ³J = 4.9 Hz, 4 H, H_β) ppm.

¹³C NMR (150 MHz, CDCl₃): δ = 13.9, 225, 29.5, 55.3, 92.1, 96.6,

113.4, 120.1, 122.3, 127.3, 130.9, 131.5, 132.6, 149.8, 151.6,

157.8 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 446 (491), 583 (3.31),

635 nm (3.93).

5,15-Bis(3-methoxyphenyl)-10,20-bis(trimethylsilanylethynyl))-

porphyrin (55): Following general procedure G, 11 (40 mg,

0.0587 mmol), ethynyltrimethylsilane (0.179 mL, 0.129 mmol), CuI

recrystallization from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.8 (2.8 mg, 0.0146 mmol), and Pd(PPh₃)₂Cl₂(4.1 mg, 0.00587 mmol)

(CH₂Cl₂/n-hexane = 2:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = were added to triethylamine (15 mL) and THF (5 mL). Purification

5810

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Eur. J. Org. Chem. 2011, 5797–5816

Porphyrins for Use in Nonlinear Optics

3

was carried out by column chromatography on silica using (n-hex-

H, H_β), 9.51 (d, J = 4.7 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz,

ane/CH₂Cl₂= 1:1, v/v) and afforded purple crystals (17.5 mg,

CDCl₃): δ = 13.96, 23.45, 34.97, 40.64, 101.73, 117.61, 121.50,

124.05, 125.58, 126.14, 127.73, 128.44, 132.52, 132.74, 136.69,

139.08 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 424 (5.01), 519 (3.76),

555 (3.42), 598 (3.33), 651 nm (3.16). HRMS (MS ES⁺) m/z calcd.

0.024 mmol, 42%); m.p. Ͼ 300 °C; R_f= 0.6 (n-hexane/CH₂Cl₂

=

1:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.16 (s, 2 H, NH),

0.62 [s, 18 H, Si(CH₃)₃], 4.03 (s, 6 H, OCH₃), 7.38 (m, 2 H, Ar-H),

3

7.69 (m, 2 H, Ar-H), 7.76 (s, 2 H, Ar-H), 7.80 (d, J = 7.2 Hz, 2 for [C₄₄H₃₄N₄Br] [M + H⁺]: 697.1967; found 697.1951.

3

H, Ar-H), 8.89 (d, J = 4.9 Hz, 4 H, H_β), 9.62 (d, J = 4.9 Hz, 4

H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 0.1, 29.5, 55.3,

100.6, 102.5, 106.6, 113.6, 120.2, 127.5, 130.3, 131.6, 142.4,

157.9 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 433 (4.99), 541 (3.97),

581 (4.02), 617 (3.06), 677 nm (3.59). HRMS (MS ES⁺) m/z calcd.

for [C₄₄H₄₃N₄O₂Si₂] [M + H⁺]: 715.2925; found 715.2924.

5-Butyl-10,20-bis(1-naphthyl)-15-(4-nitrophenyl)porphyrin (59): Fol-

lowing general procedure C, 58 (40 mg, 0.057 mmol), K₃PO₄

(303 mg, 1.425 mmol), (4-nitrophenyl)boronic pinacol ester

(178 mg, 0.7125 mmol), and Pd(PPh₃)₄(6.6 mg, 0.0057 mmol) in

THF (40 mL) gave 25 mg (0.033 mmol, 60%) of a purple solid after

recrystallization from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.5

1

[5,15-Bis(3-methoxyphenyl)-10,20-bis(trimethylsilanylethynyl)-

porphyrinato]zinc(II) (56): Following general procedure G, 35

(CH₂Cl₂: n-hexane = 1:1, v/v). H NMR (600 MHz, CDCl₃): δ =

3

–2.39 (s, 2 H, NH), 1.13 (t, J = 7.5 Hz, 3 H, CH₂CH₂CH₂CH₃),

(40 mg, 0.053 mmol), ethynyltrimethylsilane (0.163 mL, 1.83 (m, 2 H, CH₂CH₂CH₂CH₃), 2.55 (m, 2 H, CH₂CH₂CH₂CH₃),

0.1183 mmol), CuI (2.5 mg, 0.01325 mmol), and Pd(PPh₃)₂Cl₂

(3.7 mg, 0.0053 mmol) were added to triethylamine (15 mL) and

THF (5 mL). Purification by column chromatography on silica gel

(n-hexane/CH₂Cl₂= 1:1, v/v) gave 25 mg (0.032 mmol, 60%) of a

purple solid; m.p. Ͼ 300 °C; R_f= 0.47 (n-hexane/CH₂Cl₂= 1:1, v/

5.00 (t, ³J = 7.9 Hz, 2 H, CH₂CH₂CH₂CH₃), 7.12–7.16 (m, 2 H,

Ar-H), 7.53 (m, 2 H, Ar-H), 7.92 (m, 2 H, Ar-H), 8.19 (d, ³J =

3

7 Hz, 2 H, Ar-H), 8.29 (d, J = 6.8 Hz, 2 H, Ar-H), 8.32 (d, J =

3

6.8 Hz, 2 H, Ar-H), 8.36 (m, 4 H, Ar-H), 8.59 (d, J = 8.6 Hz, 2

3

H, Ar-H), 8.61 (s, 4 H, H_β), 8.69 (d, J = 4 Hz, 2 H, H_β), 9.42 (d,

1

v). H NMR (400 MHz, CDCl₃): δ = 0.63 (s, 18 H, CH₃), 3.98 (s,

³J = 4.9 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ =

6 H, OCH₃), 7.34 (d, ³J = 8.2 Hz, 2 H, Ar-H), 7.67 (t, ³J = 7.6 Hz, 14.14, 23.65, 35.19, 40.96, 115.86, 117.65, 121.79, 124.21, 125.72,

3

2 H, Ar-H), 7.73 (s, 2 H, Ar-H), 7.79 (d, J = 7.6 Hz, 2 H, Ar-H), 126.27, 127.90, 128.61, 131.94, 132.67, 132.90, 135.04, 136.85,

3

8.98 (d, J = 4.7 Hz, 4 H, H_β), 9.71 (d, ³J = 4.7 Hz, 4 H, H_β) ppm. 139.36, 147.63, 148.95 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 423

¹³C NMR (150 MHz, CDCl₃): δ = 0.3, 29.5, 55.3, 101.8, 107.2, (4.97), 518 (3.80), 552 (3.48), 594 (3.36), 647 nm (3.27). HRMS

113.4, 122.2, 127.4, 132.6, 149.9, 152.1, 157.7 ppm. UV/Vis

(MS ES⁺) m/z calcd. for [C₅₀H₃₈N₅O₂] [M + H⁺]: 740.3026; found

(CH₂Cl₂): λ_max(logε) = 446 (5.07), 583 (3.41), 653 nm (4.09).

740.3006.

10-Butyl-5,15-bis(1-naphthyl)porphyrin (57): Following general pro-

cedure H, 3 (300 mg, 0.533 mmol) was dissolved in dry THF

(80 mL) under an argon atmosphere and the reaction mixture was

cooled down to –78 °C. nBuLi (2.13 mL, 5.33 mmol) was added

dropwise over 15 min by syringe. The cold bath was removed and

stirring continued for 14 h at room temperature, followed by ad-

dition of H₂O (0.5 mL). Stirring continued for 15 min and then

DDQ (1.2 g, 5.33 mmol) was added in THF (10 mL). The reaction

mixture was stirred for an additional hour to give 180 mg

(0.29 mmol, 55 %) of a purple solid after recrystallization from

CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.42 (CH₂Cl₂/n-hexane = 1:1,

v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.70 (s, 2 H, NH), 1.13 (t,

³J = 7.6, 3 H, 6.4 Hz, CH₂CH₂CH₂CH₃), 1.82 (m, 2 H,

5-Butyl-15-(4-cyanophenyl)-10,20-bis(1-naphthyl)porphyrin (60):

Following general procedure C, 58 (40 mg, 0.057 mmol), K₃PO₄

(303 mg, 1.425 mmol), (4-cyanophenyl)boronic acid (105 mg,

0.7125 mmol), and Pd(PPh₃)₄(6.6 mg, 0.0057 mmol) in THF

(40 mL) gave 23 mg (0.031 mmol, 56 %) of a purple solid after

recrystallization from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.32

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

–2.42 (s, 2 H, NH), 1.16 (m, 3 H, CH₂CH₂CH₂CH₃), 1.81 (m, 2

H, CH₂CH₂CH₂CH₃), 2.54 (m, 2 H, CH₂CH₂CH₂CH₃), 4.98 (t, ³J

= 7.6, 2 H, 8.18 Hz, CH₂CH₂CH₂CH₃), 7.13 (m, 4 H, Ar-H), 7.53

(m, 2 H, Ar-H), 7.91 (t, ³J = 8.2 Hz, 2 H, Ar-H), 8.03 (d, ³J =

3

8.2 Hz, 2 H, Ar-H), 8.20 (d, J = 8.8 Hz, 2 H, Ar-H), 8.32 (m, 6

3

H, Ar-H), 8.61 (s, 4 H, H_β), 8.69 (d, J = 4.7 Hz, 2 H, H_β), 9.42

3

CH₂CH₂CH₂CH₃), 2.55 (m, 2 H, CH₂CH₂CH₂CH₃), 5.06 (m, 2 H, (d, J = 4.7 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ =

CH₂CH₂CH₂CH₃), 7.13–7.19 (m, 4 H, Ar-H), 7.54 (t, ³J = 8.2. 8.8, 13.73, 23.22, 30.51, 34.74, 40.52, 111.25, 115.94, 117.11, 118.61,

3

6.4 Hz, 2 H, Ar-H), 7.93 (m, 2 H, Ar-H), 8.20 (d, J = 8.2 Hz, 2

121.21, 123.78, 125.28, 127.99, 128.15, 129.77, 130.08, 131.40,

3

H, Ar-H), 8.32 (d, J = 7 Hz, 2 H, Ar-H), 8.36 (d, J = 7.6 Hz, 2 132.23, 134.47, 136.36, 138.91, 146.47 ppm. UV/Vis (CH₂Cl₂): λ_max

3

H, Ar-H), 8.72 (m, 4 H, H_β), 9.19 (d, J = 4.7 Hz, 2 H, H_β), 9.47

(logε) = 424 (4.91), 516 (3.78), 552 (3.43), 590 (3.44), 648 nm (3.25).

(d, ³J = 4.7 Hz, 2 H, H_β), 10.07 (s, 1 H, H_meso) ppm. ¹³C NMR HRMS (MS ES⁺) m/z calcd. for [C₅₁H₃₈N₅] [M + H⁺]: 720.3127;

(150 MHz, CDCl₃): δ = 14.19, 23.70, 35.53, 41.09, 104.04, 116.56, found 720.3121.

121.26, 124.28, 125.69, 126.19, 127.87, 128.68, 131.11, 132.73,

5-Butyl-15-(4-methoxycarbonylphenyl)-10,20-bis(1-naphthyl)-

porphyrin (61): Following general procedure C, 58 (40 mg,

0.057 mmol), K₃PO₄(303 mg, 1.425 mmol), (4-methoxycarbon-

ylphenyl)boronic acid (128 mg, 0.7125 mmol), and Pd(PPh₃)₄

136.87, 139.28 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 414 (5.11),

509 (3.90), 545 (3.42), 584 (3.48), 640 nm (3.18). HRMS (MS ES⁺)

m/z calcd. for [C₄₄H₃₅N₄] [M + H⁺]: 619.2862; found 619.2859.

5-Bromo-15-butyl-10,20-bis(1-naphthyl)porphyrin (58): Following (6.6 mg, 0.0057 mmol) in THF (40 mL) gave 18 mg (0.023 mmol,

general procedure B, 57 (150 mg, 0.242 mmol) and NBS (46 mg,

42 %) of a purple solid after recrystallization from CH₂Cl₂/

0.254 mmol) gave 155 mg (0.22 mmol, 92%) of a purple solid after

CH₃OH; m.p. Ͼ300 °C; R_f= 0.32 (CH₂Cl₂/n-hexane = 1:1, v/v).

3

recrystallization from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.4 ¹H NMR (400 MHz, CDCl₃): δ = –2.41 (s, 2 H, NH), 1.13 (t, J =

(CH₂Cl₂/n-hexane = 1:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = 7 Hz, 3 H, CH₂CH₂CH₂CH₃), 1.83 (m, 2 H, CH₂CH₂CH₂CH₃),

–2.39 (s, 2 H, NH), 1.11 (t, ³J = 7.6, 3 H, 7 Hz, CH₂CH₂CH₂CH₃),

2.55 (m, 2 H, CH₂CH₂CH₂CH₃), 4.10 (s, 3 H, COOCH₃), 4.99 (t,

1.81 (m, 2 H, CH₂CH₂CH₂CH₃), 2.51 (m, 2 H, CH₂CH₂CH₂CH₃), ³J = 7.6, 2 H, 8.2 Hz, CH₂CH₂CH₂CH₃), 7.14 (m, 4 H, Ar-H),

4.93 (t, ³J = 7.6, 2 H, 7 Hz, CH₂CH₂CH₂CH₃), 7.13 (t, ³J = 8.2 Hz, 7.53 (t, ³J = 7.6, 2 H, 6.4 Hz, Ar-H), 7.91 (m, 2 H, Ar-H), 8.19 (d,

3

4 H, Ar-H), 7.54 (m, 2 H, Ar-H), 7.92 (m, 2 H, Ar-H), 8.19 (d, J

³J = 8.8 Hz, 2 H, Ar-H), 8.30 (m, 4 H, Ar-H), 8.34 (d, ³J = 8.2 Hz,

3

= 8.2 Hz, 2 H, Ar-H), 8.29 (m, 2 H, Ar-H), 8.35 (d, J = 8.2 Hz, 2 2 H, Ar-H), 8.41 (d, J = 7.6 Hz, 2 H, Ar-H), 8.59 (d, J = 4.7 Hz,

H, Ar-H), 8.62 (d, J = 4.7 Hz, 4 H, H_β), 9.36 (d, J = 4.7 Hz, 2

2 H, H_β), 8.68 (d, ³J = 4.7 Hz, 4 H, H_β), 9.42 (d, ³J = 4.7 Hz, 2 H,

3

Eur. J. Org. Chem. 2011, 5797–5816

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5811

M. O. Senge, M. Fazekas, M. Pintea, M. Zawadzka, W. J. Blau

FULL PAPER

3

H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 14.00, 23.50, 35.01, CH₂CH₂CH₂CH₃), 2.55 (m, 2 H, CH₂CH₂CH₂CH₃), 4.99 (t, J =

40.77, 52.19, 117.17, 121.08, 124.05, 125.53, 126.09, 127.71, 128.54, 7.8, 2 H, 8.8 Hz, CH₂CH₂CH₂CH₃), 7.11 (m, 4 H, Ar-H), 7.38 (m,

3

129.31, 132.51, 132.74, 134.34, 136.69, 139.39, 146.61 ppm. UV/Vis

2 H, Ar-H), 7.55 (m, 5 H, Ar-H), 7.94 (m, 2 H, Ar-H), 7.99 (d, J

(CH₂Cl₂): λ_max(log ε) = 422 (4.90), 518 (3.70), 552 (3.40), 593 = 7.8 Hz, 2 H, Ar-H), 8.20 (d, ³J = 8.8 Hz, 2 H, Ar-H), 8.35 (d, ³J

(3.41), 646 nm (3.22). HRMS (MS ES⁺) m/z calcd. for = 8.8 Hz, 2 H, Ar-H), 8.70 (d, J = 3.9 Hz, 4 H, H_β), 9.45 (d, J =

3

[C₅₂H₄₁N₄O₂] [M + H⁺]: 753.3230; found 753.3226.

3.9 Hz, 2 H, H_β), 9.71 (d, J = 4.9 Hz, 2 H, H_β) ppm. ¹³C NMR

(150 MHz, CDCl₃): δ = 14.00, 23.60, 35.37, 40.93, 92.17, 95.80,

118.87, 124.05, 125.46, 125.96, 127.70, 128.27, 128.48, 129.17,

130.75, 131.98, 132.34, 132.61, 136.69, 139.66, 150.00, 150.47,

152.43 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 438 (4.98), 566 (3.74),

606 nm (3.69). HRMS (MS ES⁺) m/z calcd. for [C₅₂H₃₆N₄Zn]:

828.2231; found 828.2270.

3

[5-Bromo-15-butyl-10,20-bis(1-naphthyl)porphyrinato]zinc(II) (62):

Following general procedure D, 58 (100 mg, 0.143 mmol) was dis-

solved in dry CH₂Cl₂(20 mL) and zinc acetate dihydrate (188 mg,

0.860 mmol) dissolved in CH₃OH was added to the reaction mix-

ture to yield 98 mg (0.129 mmol, 90%) after recrystallization from

CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.5 (CH₂Cl₂: n-hexane = 1:1,

1

3

v/v). H NMR (400 MHz, CDCl₃): δ = 1.14 (t, J = 7.6 Hz, 3 H, 5-(4-Methoxycarbonylphenyl)-10,20-bis(1-naphthyl)-20-(3-thio-

CH₂CH₂CH₂CH₃), 1.85 (m, 2 H, CH₂CH₂CH₂CH₃), 2.55 (m, 2 H, phenyl)porphyrin (65): Following general procedure C, 10 (50 mg,

C H ₂C H ₂C H ₂C H ₃) , 4 . 9 8 ( t , ³J = 7 . 6 , 2 H , 8 . 2 H z , 0.07 mmol), (4-methoxycarbonylphenyl)boronic acid (63 mg,

CH₂CH₂CH₂CH₃), 7.07 (m, 4 H, Ar-H), 7.52 (m, 2 H, Ar-H), 7.92 0.35 mol), (thiophen-3-yl)boronic acid (45 mg, 0.35 mmol),

(m, 2 H, Ar-H), 8.19 (d, ³J = 8.8 Hz, 2 H, Ar-H), 8.29 (m, 2 H, Pd(PPh₃)₄(8 mg, 0.007 mmol), and K₃PO₄(293 mg, 1.38 mmol) in

Ar-H), 8.34 (d, ³J = 8.8 Hz, 2 H, Ar-H), 8.67 (d, ³J = 4.7 Hz, 4 H,

THF (40 mL) gave 7 mg (0.009 mmol, 16%) of a purple solid after

recrystallization from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.2

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

3

H_β), 9.45 (d, J = 3.5 Hz, 2 H, H_β), 9.59 (d, J = 4.7 Hz, 2 H, H_β)

ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 14.21, 23.78, 35.54, 41.24,

118.45, 122.42, 124.06, 125.60, 126.07, 127.85, 128.26, 128.74, –2.12 (s, 2 H, NH), 4.14 (s, 3 H, COOCH₃), 7.16–7.23 (m, 4 H,

129.43, 131.63, 132.65, 132.99, 136.94, 140.17, 149.82, 150.54, Ar-H), 7.56 (t, ³J = 7.6 Hz, 2 H, Ar-H), 7.71 (t, ³J = 8.2, 2 H,

3

150.79 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 425 (4.81), 555 (3.53),

6.4 Hz, Ar-H), 7.86 (d, J = 7 Hz, 2 H, Ar-H), 7.90 (s, 1 H, Ar-H),

597 nm (2.92). HRMS (MS ES⁺) m/z calcd. for [C₄₄H₃₁N₄BrZn] 7.95 (t, J = 7 Hz, 2 H, Ar-H), 8.14 (d, J = 7.6 Hz, 2 H, Ar-H),

3

(M⁺): 758.1072; found 758.1057.

8.62 (d, J = 8.2 Hz, 2 H, Ar-H), 8.75 (d, J = 4.7 Hz, 4 H, H_β),

9.06 (t, J = 8.2 Hz, 4 H, Ar-H), 9.38 (d, J = 5.3 Hz, 2 H, H_β),

9.50 (d, J = 4.7 Hz, 2 H, H_β) ppm. UV/Vis (CH₂Cl₂): λ_max(logε)

= 422 (5.04), 515 (3.81), 551 (3.47), 592 (3.44), 645 nm (3.30).

HRMS (MS ES⁺) m/z calcd. for [C₅₂H₃₅N₄O₂S] [M + H⁺]:

779.2481; found 779.2508.

3

[5-Butyl-10,20-bis(1-naphthyl)-15-{2-(3-nitrophenyl)vinyl}por-

phyrinato]zinc(II) (63): Following general procedure F, 62 (50 mg,

0.065 mmol), 3-nitrostyrene (0.3 mL, 2.3 mmol), NaOAc (30 mg,

0.364 mmol), Pd(OAc)₂(1.5 mg, 0.0065 mmol), and PPh₃(6.8 mg,

0.026 mmol) were added to DMF (50 mL) and heated at 120 °C for

16 h. The crude product was purified by column chromatography

(CH₂Cl₂/n-hexane = 2:1, v/v) to give 25 mg (0.030 mmol, 46%) of

a purple solid after recrystallization from CH₂Cl₂/CH₃OH; m.p.

Ͼ300 °C; R_f= 0.23 (CH₂Cl₂/n-hexane = 1:1, v/v). ¹H NMR

3

5,15-Bis(1-naphthyl)-10-(4-nitrophenyl)-20-(3-thiophenyl)porphyrin

(66): Following general procedure C, 10 (50 mg, 0.07 mmol), pin-

acol (4-nitrophenyl)boronate (120 mg, 0.483 mmol), (thiophen-3-yl)-

boronic acid (62 mg, 0.487 mmol), Pd(PPh₃)₄(8 mg, 0.007 mmol),

( 4 0 0 M H z , C D C l ₃) : δ = 1 . 1 5 ( t , ³J = 7 . 6 H z , 3 H , and K₃PO₄(368 mg, 1.735 mmol) in THF (40 mL) gave 10 mg

CH₂CH₂CH₂CH₃), 1.87 (m, 2 H, CH₂CH₂CH₂CH₃), 2.57 (m, 2 H, (0.013 mmol, 19%) of a purple solid after recrystallization from

C H ₂C H ₂C H ₂C H ₃) , 4 . 9 9 ( t , ³J = 7 . 6 , 2 H , 8 . 7 H z , CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.2 (CH₂Cl₂/n-hexane = 1:1,

CH₂CH₂CH₂CH₃), 7.04–7.15 (m, 4 H, Ar-H), 7.37 (d, ³J =

v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.39 (s, 2 H, NH), 7.13 (t,

15.8 Hz, 1 H, alkene-H), 7.50–7.55 (m, 2 H, Ar-H), 7.68 (t, ³J = ³J = 6.4 Hz, 4 H, Ar-H), 7.53 (m, 2 H, Ar-H), 7.72 (t, J = 8.2 Hz,

3

8.2 Hz, 1 H, Ar-H), 7.93 (t, J = 8.8 Hz, 2 H, Ar-H), 8.14 (d, J =

2 H, Ar-H), 7.92 (t, ³J = 8.2 Hz, 2 H, Ar-H), 8.01 (m, 1 H, Ar-H),

3

7 Hz, 2 H, Ar-H), 8.19 (d, J = 8.2 Hz, 2 H, Ar-H), 8.25 (d, J = 8.03 (m, 1 H, Ar-H), 8.19 (d, J = 8.2 Hz, 2 H, Ar-H), 8.30 (d, J

3

6.4 Hz, 1 H, Ar-H), 8.30 (d, J = 6.4 Hz, 1 H, Ar-H), 8.34 (m, 3

= 7.6 Hz, 1 H, Ar-H), 8.34 (d, ³J = 8.2 Hz, 3 H, Ar-H), 8.40 (d, ³J

= 8.2 Hz, 2 H, Ar-H), 8.64 (m, 7 H, overlapped Ar-H, H_β), 8.93

3

H, Ar-H), 8.73 (m, 4 H, H_β), 9.42 (d, J = 4.7 Hz, 2 H, H_β), 9.49

(d, ³J = 4.7 Hz, 2 H, H_β), 9.74 (d, ³J = 15.8 Hz, 1 H, alkene-H)

ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 14.03, 23.63, 35.33, 40.98,

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

3

115.45, 116.78, 118.26, 121.86, 123.67, 124.26, 125.76, 126.33,

115.24, 118.36, 121.02, 122.22, 124.06, 125.46, 127.73, 128.35, 127.93, 128.52, 128.88, 131.46, 132.74, 134.42, 135.05, 136.77,

128.55, 129.18, 129.70, 132.16, 132.75, 136.73, 139.15, 139.84, 139.05, 141.76, 147.68, 148.95 ppm. UV/Vis (CH₂Cl₂): λ_max(logε)

148.84, 149.38, 150.25 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 430

(5.09), 560 (3.86), 604 nm (3.53). MS (ES⁺): m/z (%) = 827 (100%),

[C₅₂H₃₇N₅O₂Zn] (M⁺).

= 423 (5.02), 517 (3.75), 553 (3.23), 592 (3.14), 646 nm (2.30).

HRMS (MS ES⁺) m/z calcd. for [C₅₀H₃₂N₅O₂S] [M + H⁺]:

766.2277; found 766.2278.

[5-Butyl-10,20-bis(1-naphthyl)-15-(phenylethynyl)porphyrinato]-

zinc(II) (64): Following general procedure G, 62 (50 mg,

0.065 mmol), phenylacetylene (0.08 mL 0.072 mmol), CuI (3 mg,

0.016 mmol), and Pd(PPh₃)₂Cl₂(4.6 mg, 0.0065 mmol) were added

to a mixture of THF (5 mL) and triethylamine (15 mL). After

10 min, the cold bath was removed and the reaction mixture was

stirred for 24 h at room temp. The crude product was purified by

flash column chromatography eluting with CH₂Cl₂/n-hexane = 1:2

(v/v) to give 21 mg (0.026 mmol, 41 %) of a purple solid after

5-(2-Benzothiophenyl)-10,20-bis(1-naphthyl)-15-(4-nitrophenyl)-

porphyrin (67): Following general procedure C, 10 (50 mg,

0.07 mmol), (4-nitrophenyl)boronic acid (120 mg, 0.483 mol), (thi-

anaphthenyl)boronic acid (86 mg, 0.483 mmol), Pd(PPh₃)₄(8 mg,

0.007 mmol), and K₃PO₄(368 mg, 1.735 mmol) in THF (40 mL)

gave 8 mg (0.010 mmol, 15%) of a purple solid after recrystalli-

zation from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.3 (CH₂Cl₂/n-

hexane = 1:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.42 (s, 2

3

H, NH), 7.14 (m, 4 H, Ar-H), 7.54 (m, 2 H, Ar-H), 7.61 (t, J =

3

recrystallization from CH₂Cl₂/CH₃OH; m.p. Ͼ300 °C; R_f= 0.5 8.8, 2 H, 7.6 Hz, Ar-H), 7.91 (t, J = 7.6 Hz, 2 H, Ar-H), 8.09 (t,

(CH₂Cl₂/n-hexane = 1:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = ³J = 6.4 Hz, 2 H, Ar-H), 8.14 (s, 1 H, Ar-H), 8.19 (d, J = 8.2 Hz,

3

1.15 (t, ³J = 6.9, 3 H, 8.8 Hz, CH₂CH₂CH₂CH₃), 1.85 (m, 2 H, 2 H, Ar-H), 8.29 (d, J = 7.6 Hz, 2 H, Ar-H), 8.34 (d, J = 8.8 Hz,

3

5812

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Eur. J. Org. Chem. 2011, 5797–5816

Porphyrins for Use in Nonlinear Optics

3

2 H, Ar-H), 8.40 (d, J = 8.2 Hz, 2 H, Ar-H), 8.63 (m, 8 H, Ar-H,

0.05 mmol), (4-methoxycarbonylphenyl)boronic acid (112 mg,

3

H_β), 9.08 (d, J = 4.7 Hz, 2 H, H_β) ppm. UV/Vis (CH₂Cl₂): λ_max0.625 mmol), Pd(PPh₃)₄(7.2 mg, 0.00625 mmol), and K₃PO₄

(logε) = 425 (4.98), 516 (3.68), 555 (3.29), 590 (3.18), 648 nm (2.46). (265 mg, 1.25 mmol) in THF (50 mL) were used. Purification by

HRMS (MS ES⁺) m/z calcd. for [C₅₄H₃₄N₅O₂S] [M + H⁺]:

column chromatography on silica gel (n-hexane/CH₂Cl₂= 1:1, v/

v) followed by recrystallization from CH₂Cl₂/CH₃OH afforded the

desired compound (15 mg, 0.021 mmol, 42%) as purple crystals;

816.2433; found 816.2467.

5,15-Bis(1-naphthyl)-10-(4-methoxycarbonylphenyl)-20-[(E)-2-

phenylethenyl]porphyrin (68): Following general procedure C, 10

(60 mg, 0.083 mmol), (4-methoxycarbonylphenyl)boronic acid

(75 mg, 0.415 mol), trans-β-styrylboronic acid (62 mg,

0.415 mmol), Pd(PPh₃)₄(10 mg, 0.0083 mmol), and K₃PO₄

(352 mg, 1.66 mmol) in THF (40 mL) gave 8 mg (0.010 mmol,

14 %) of a purple solid after recrystallization from CH₂Cl₂/

1

m.p. Ͼ 300 °C; R_f= 0.25 (n-hexane/CH₂Cl₂= 1:1, v/v). H NMR

3

(400 MHz, CDCl₃): δ = –2.72 (s, 2 H, NH), 1.15 (t, J = 7.6 Hz, 3

H, CH₂CH₂CH₂CH₃), 1.85 (m, 2 H, CH₂CH₂CH₂CH₃), 2.56 (m,

2 H, CH₂CH₂CH₂CH₃), 4.02 (s, 6 H, OCH₃), 4.13 (s, 3 H, OCH₃),

3

5.06 (t, J = 8.2 Hz, 2 H, CH₂CH₂CH₂CH₃), 7.37 (m, 2 H, Ar-H),

3

7.6 (t, J = 7.6 Hz, 2 H, Ar-H), 7.81 (m, 4 H, Ar-H), 8.30 (d, J =

3

7.6 Hz, 2 H, Ar-H), 8.45 (d, J = 7.6 Hz, 2 H, Ar-H), 8.75 (d, J

1

CH₃OH; m.p. Ͼ300 °C; R_f= 0.2 (CH₂Cl₂/n-hexane = 1:1, v/v). H

NMR (400 MHz, CDCl₃): δ = –2.24 (s, 2 H, NH), 4.09 (s, 3 H,

3

= 4.7 Hz, 2 H, H_β), 8.88 (d, J = 4.7 Hz, 2 H, H_β), 8.99 (d, J =

4.7 Hz, 2 H, H_β), 9.52 (d, J = 4.7 Hz, 2 H, H_β) ppm. ¹³C NMR

3

COOCH₃), 7.12–7.16 (m, 4 H, Ar-H), 7.41 (d, J = 15.8 Hz, 1 H,

(100 MHz, CDCl₃): δ = 13.7, 23.2, 29.2, 34.8, 40.5, 55.0, 113.0,

117.2, 119.9, 120.7, 127.0, 127.1, 127.5, 128.9, 134.1, 143.1, 157.4,

166.9 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 419 (4.92), 516 (3.57),

551 (3.30), 593 (3.22), 648 nm (3.18). HRMS (MS ES⁺) m/z calcd.

for [C₄₆H₃₈N₅O₂] [M + H⁺]: 713.3107; found 713.3128.

alkene-H), 7.53 (t, ³J = 7, 2 H, 6.4 Hz, Ar-H), 7.58 (t, ³J = 7.6 Hz,

3

2 H, Ar-H), 7.93 (m, 4 H, Ar-H), 8.18 (d, J = 8.7 Hz, 2 H, Ar-

H), 8.28 (d, ³J = 8.2 Hz, 2 H, Ar-H), 8.33 (t, ³J = 7.6 Hz, 4 H, Ar-

H), 8.41 (d, ³J = 8.2 Hz, 2 H, Ar-H), 8.58 (d, ³J = 4.7 Hz, 2 H,

H_β), 8.67 (d, ³J = 4.7 Hz, 4 H, H_β), 9.44 (d, J = 4.7 Hz, 2 H, H_β),

3

9.62 (d, ³J = 15.8 Hz, 1 H, alkene-H) ppm. UV/Vis (CH₂Cl₂): λ_max

(logε) = 424 (5.01), 516 (3.78), 553 (3.44), 591 (3.37), 647 nm (3.31).

HRMS (MS ES⁺) m/z calcd. for [C₅₆H₃₉N₄O₂] [M + H⁺]: 799.3073;

found 799.3064.

5-Butyl-15-(4-cyanophenyl)-10,20-bis(3-methoxyphenyl)porphyrin

(72): Following general procedure C, 69 (32.8 mg, 0.05 mmol), (4-

cyanophenyl)boronic acid (91.8 mg, 0.625 mmol), Pd(PPh₃)₄

(7.2 mg, 0.00625 mmol), and K₃PO₄(265 mg, 1.25 mmol) in THF

(50 mL) were used. Purification by column chromatography on sil-

ica gel (n-hexane/CH₂Cl₂= 1:1, v/v) followed by recrystallization

from CH₂Cl₂/CH₃OH afforded the desired compound (7 mg,

0.025 mmol, 43%) as purple crystals; m.p. Ͼ 300 °C; R_f= 0.15 (n-

hexane/CH₂Cl₂= 1:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.73

5-Bromo-15-butyl-10,20-bis(3-methoxyphenyl)porphyrin (69): Fol-

lowing general procedure B, 5-butyl-10,20-bis(3-methoxyphen-

yl)porphyrin (60 mg, 0.094 mmol), NBS (20.2 mg, 0.11 mmol), pyr-

idine (1.0 mL) and acetone (10 mL) in dry CH₂Cl₂were used. Puri-

fication of the product was carried out by filtration through a silica

gel column using CH₂Cl₂followed by recrystallization from

CH₂Cl₂/CH₃OH afforded the desired compound (50 mg,

0.76 mmol, 80%) as purple crystals; m.p. Ͼ 300 °C; R_f= 0.8 (n-

hexane/CH₂Cl₂= 2:1, v/v). ¹H NMR (400 MHz, CDCl₃): δ = –2.73

3

(s, 2 H, NH), 1.16 (t, J = 7 Hz, 3 H, CH₂CH₂CH₂CH₃), 1.85 (m,

2 H, CH₂CH₂CH₂CH₃), 2.56 (m, 2 H, CH₂CH₂CH₂CH₃), 4.02 (s,

6 H, OCH₃), 5.06 (t, ³J = 7.6 Hz, 2 H, CH₂CH₂CH₂CH₃), 7.38 (d,

3

³J = 8.3 Hz, 2 H, Ar-H), 7.68 (t, J = 7.6 Hz, 1 H, Ar-H), 7.81 (m,

3

4 H, Ar-H), 8.08 (d, J = 8.2 Hz, 2 H, Ar-H), 8.33 (d, J = 7.6 Hz,

3

(s, 2 H, NH), 1.14 (t, J = 7 Hz, 3 H, CH₂CH₂CH₂CH₃), 1.83 (m,

3

2 H, Ar-H), 8.69 (d, J = 4.1 Hz, 2 H, H_β), 8.90 (d, J = 4.7 Hz, 2

2 H, CH₂CH₂CH₂CH₃), 2.52 (m, 2 H, CH₂CH₂CH₂CH₃), 4.03 (s,

3

H, H_β), 8.99 (d, J = 4.7 Hz, 2 H, H_β), 9.53 (d, J = 4.7 Hz, 2 H,

H_β) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 14.2, 18.4, 35.3, 41.0,

55.5, 11.7, 113.5, 116.3, 119.7, 120.4, 121.6, 127.4, 130.5, 134.9,

143.4, 145.2, 154.6, 157.9 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 419

(4.98), 516 (3.63), 551 (3.34), 592 (3.28), 648 nm (3.21). HRMS

(MS ES⁺) m/z calcd. for [C₄₅H₃₈N₅O₂] [M + H⁺]: 680.3026; found

680.2999.

3

6 H, OCH₃), 4.98 (t, J = 8 Hz, 2 H, CH₂CH₂CH₂CH₃), 7.38 (m,

3

2 H, Ar-H), 7.68 (t, J = 8 Hz, 2 H, Ar-H), 7.79 (m, 4 H, Ar-H),

3

8.93 (t, J = 5.5 Hz, 4 H, H_β), 9.46 (d, J = 4.5 Hz, 2 H, H_β), 9.62

(d, J = 4.5 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ =

3

13.7, 23.1, 34.8, 40.4, 55.0, 113.1, 119.4, 119.9, 121.1, 127.0, 142.8,

157.4 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 421 (4.73), 518 (3.40),

554 (3.17), 596 (3.01), 657 nm (2.96). HRMS (MS ES⁺) m/z calcd.

for [C₃₈H₃₄N₄O₂Br] [M + H⁺]: 657.1865; found 657.1862.

5-Butyl-10,20-bis(3-methoxyphenyl)-15-(4-nitrophenyl)porphyrin

(73): Following general procedure C, 69 (32.8 mg, 0.05 mmol), pin-

acol (4-nitrophenyl)boronate (156 mg, 0.625 mmol), Pd(PPh₃)₄

(7.2 mg, 0.00625 mmol), and K₃PO₄(265 mg, 1.25 mmol) in THF

(50 mL) were used. Purification by column chromatography on sil-

ica gel (n-hexane/CH₂Cl₂= 1:1, v/v) followed by recrystallization

from CH₂Cl₂/CH₃OH gave purple crystals (25 mg, 0.035 mmol,

[5-Bromo-15-butyl-10,20-bis(3-methoxyphenyl)porphyrinato]zinc(II)

(70): Following general procedure D, 69 (100 mg, 0.152 mmol) and

zinc acetate dihydrate (167 mg, 0.912 mmol) in dry CH₂Cl₂(20 mL)

gave a purple solid after recrystallization from CH₂Cl₂/MeOH

(85 mg, 0.117 mmol, 77%); m.p. Ͼ 300 °C; R_f= 0.16 (CH₂Cl₂/n-

1

3

hexane = 1:1, v/v). H NMR (400 MHz, CDCl₃): δ = 1.16 (t, J =

7.5 Hz, 3 H, CH₂CH₂CH₂CH₃), 1.86 (m, 2 H, CH₂CH₂CH₂CH₃),

1

71%); m.p. Ͼ 300 °C; R_f= 0.42 (n-hexane/CH₂Cl₂= 1:1, v/v). H

NMR (400 MHz, CDCl₃): δ = –2.71 (s, 2 H, NH), 1.16 (t, ³J =

7.6 Hz, 3 H, CH₂CH₂CH₂CH₃), 1.85 (m, 2 H, CH₂CH₂CH₂CH₃),

3

2.53 (m, 2 H, CH₂CH₂CH₂CH₃), 3.99 (s, 6 H, OCH₃), 4.94 (t, J

= 8 Hz, 2 H, CH₂CH₂CH₂CH₃), 7.34 (m, 2 H, Ar-H), 7.68 (t, J

= 7.8 Hz, 2 H, Ar-H), 7.79 (d, J = 7 Hz, 2 H, Ar-H), 8.99 (dd, J

3

2.56 (m, 2 H, CH₂CH₂CH₂CH₃), 4.02 (s, 6 H, OCH₃), 5.06 (t, J

3

= 7.6, 2 H, Hz, CH₂CH₂CH₂CH₃), 7.38 (m, 2 H, Ar-H), 7.68 (t,

3

= 2.5 Hz, 4 H, H_β), 9.51 (d, J = 4.8 Hz, 2 H, H_β), 9.70 (d, J =

4.8 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 14.2,

23.7, 35.4, 41.1, 55.5, 113.4, 120.3, 120.7, 127.3, 127.5, 129.2, 132.5,

133.1, 143.8, 149.7, 150.0, 150.5, 157.7 ppm. UV/Vis (CH₂Cl₂):

λ_max(logε) = 422 (5.19), 553 (3.93), 593 nm (3.46). HRMS (MS

ES⁺) m/z calcd. for [C₃₈H₃₁N₄O₂BrZn] (M⁺): 718.0936; found

718.0922.

³J = 7.6 Hz, 2 H, Ar-H), 7.81 (m, 4 H, Ar-H), 8.39 (d, ³J = 8.8 Hz,

3

2 H, Ar-H), 8.65 (d, J = 8.8 Hz, 2 H, Ar-H), 8.70 (d, J = 4.7 Hz,

3

2 H, H_β), 8.91 (d, J = 4.7 Hz, 2 H, H_β), 9.0 (d, J = 4.7 Hz, 2 H,

H_β), 9.53 (d, ³J = 4.7 Hz, 2 H, H_β) ppm. ¹³C NMR (150 MHz,

CDCl₃): δ = 14.2, 23.6, 35.3, 41.0, 53.5, 113.5, 115.8, 119.8, 120.4,

121.9, 127.5, 127.9, 135.1, 143.4, 147.6, 149.1, 157.9 ppm. UV/Vis

(CH₂Cl₂): λ_max(logε) = 420 (5.08), 516 (3.8), 552 (3.47), 592 (3.34),

5-Butyl-15-(4-methoxycarbonylphenyl)-10,20-bis(3-methoxyphen- 648 nm (3.20). HRMS (MS ES⁺) m/z calcd. for [C₄₄H₃₈N₅O₄] [M

yl)porphyrin (71): Following general procedure C, 69 (32.8 mg,

+ H⁺]: 700.2924; found 700.2908.

Eur. J. Org. Chem. 2011, 5797–5816

www.eurjoc.org

5813

M. O. Senge, M. Fazekas, M. Pintea, M. Zawadzka, W. J. Blau

FULL PAPER

5-Butyl-10,20-bis(3-methoxyphenyl)-15-(phenylethynyl)porphyrin

(74): Following general procedure G, 69 (40 mg, 0.060 mmol), eth-

ynylbenzene (0.072 mL, 0.066 mmol), CuI (2.9 mg, 0.015 mmol),

and Pd(PPh₃)₂Cl₂(4.2 mg, 0.0060 mmol) were added to triethyl-

amine (15 mL) and THF (5 mL). Purification by column

chromatography on silica gel (n-hexane/CH₂Cl₂= 4:1, v/v) afforded

the desired compound (16 mg, 0.0235 mmol, 39%) as purple crys-

tals; m.p. Ͼ 300 °C; R_f= 0.37 (n-hexane/CH₂Cl₂= 1:1, v/v). ¹H

NMR (400 MHz, CDCl₃): δ = –2.24 (s, 2 H, NH), 1.15 (t, ³J = 7.3,

3 H, Hz, CH₂CH₂CH₂CH₃), 1.83 (m, 2 H, CH₂CH₂CH₂CH₃), 2.53

(m, 2 H, CH₂CH₂CH₂CH₃), 4.04 (s, 6 H, OCH₃), 4.98 (t, ³J =

8 Hz, 2 H, CH₂CH₂CH₂CH₃), 7.39 (m, 2 H, Ar-H), 7.53 (m 1 H,

167.1 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 420 (4.91), 516 (4.09),

553 (3.92), 592 (3.61), 647 nm (3.39). HRMS (MS ES⁺) m/z calcd.

for [C₅₁H₄₉N₄O₇] [M + H⁺]: 829.3601; found 829.3629.

5,15-Bis(4-cyanophenyl)-10-hexyl-20-(3,4,5-trimethoxyphenyl)-

porphyrin (78): Following general procedure C, 76 (30 mg of

0.0417 mmol),

(4-cyanophenyl)boronic

acid,

(75.6 mg,

0.521 mmol), Pd(PPh₃)₄(6 mg, 0.00521 mmol), and K₃PO₄

(221 mg, 1.739 mmol) in THF (50 mL) were used. Purification by

column chromatography on silica gel (n-hexane/ethyl acetate = 5:1,

v/v) followed by recrystallization from CH₂Cl₂/CH₃OH gave purple

crystals (16 mg, 0.02 mmol, 50%); m.p. Ͼ 300 °C; R_f= 0.15 (n-

1

hexane/ethyl acetate = 6:1, v/v). H NMR (400 MHz, CDCl₃): δ =

3

Ar-H), 7.60 (t, J = 7.5 Hz, 2 H, Ar-H), 7.70 (t, J = 7.5 Hz, 2 H,

–2.75 (s, 2 H, NH), 0.96 (t, ³J = 7 Hz, 3 H, CH₂CH₂CH₂-

CH₂CH₂CH₃), 1.42 (m, 2 H, CH₂CH₂CH₂CH₂CH₂CH₃), 1.52 (m,

2 H, CH₂CH₂CH₂CH₂CH₂CH₃), 1.85 (m, 2 H, CH₂CH₂CH₂-

CH₂CH₂CH₃), 2.58 (m, 2 H, CH₂CH₂CH₂CH₂CH₂CH₃), 3.99 (s,

6 H, OCH₃), 4.20 (s, 3 H, OCH₃), 5.06 (t, ³J = 7.6 Hz, 2 H,

3

Ar-H), 7.83 (m, 4 H, Ar-H), 8.07 (d, J = 7 Hz, 2 H, Ar-H), 8.91

3

(d, J = 4.8 Hz, 2 H, H_β), 8.94 (d, J = 4.8 Hz, 2 H, H_β), 9.44 (d,

³J = 5 Hz, 2 H, H_β), 9.71 (d, ³J = 4.8 Hz, 2 H, H_β) ppm. ¹³C NMR

(150 MHz, CDCl₃): δ = 14.2, 23.6, 29.7, 35.3, 40.8, 55.5, 91.9, 96.4,

98.6, 120.3, 127.5, 128.5, 131.6, 143.3,157.9 ppm. UV/Vis

(CH₂Cl₂): λ_max(log ε) = 433 (4.78), 532 (3.36), 575 (3.67), 610

(3.05), 668 nm (3.25). HRMS (MS ES⁺) m/z calcd. for

[C₄₆H₃₉N₄O₂] [M + H⁺]: 679.3073; found 670.3082.

3

CH₂CH₂CH₂CH₂CH₂CH₃), 8.11 (d, J = 7.6 Hz, 4 H, Ar-H), 8.36

3

(d, J = 7.6 Hz, 4 H, Ar-H), 8.72 (d, J = 4.7 Hz, 2 H, H_β), 8.84

3

(d, J = 4.7 Hz, 2 H, H_β), 8.97 (d, J = 4.7 Hz, 2 H, H_β), 9.57 (d,

³J = 4.1 Hz, 2 H, H_β) ppm. ¹³C NMR (100 MHz, CDCl₃): δ =

14.1, 22.7, 30.2, 31.9, 35.6, 39.0, 56.3, 61.3, 111.9, 112.8, 117.3,

119.0, 119.9, 121.9, 130.5, 134.9, 137.0, 137.9, 147.2, 151.5 ppm.

UV/Vis (CH₂Cl₂): λ_max(logε) = 420 (4.89), 516 (3.78), 551 (3.62),

592 (3.52), 647 nm (3.17). HRMS (MS ES⁺) m/z calcd. for

[C₄₉H₄₃N₆O₃] [M + H⁺]: 763.3397; 763.3386.

[5-Butyl-10,20-bis(3-methoxyphenyl)-15-(phenylethynyl)porphyrin-

ato]zinc(II) (75): Following general procedure G, 70 (40 mg,

0.055 mmol), phenylacetylene (0.066 mL, 0.0605 mmol), CuI

(2.6 mg, 0.01375 mmol), and Pd(PPh₃)₂Cl₂(3.8 mg, 0.0055 mmol)

were added to triethylamine (15 mL) and THF (5 mL). Purification

by column chromatography on silica gel (n-hexane/CH₂Cl₂= 2:1,

v/v) afforded the title compound as purple crystals (25 mg,

0.033 mmol, 61%); m.p. Ͼ 300 °C; R_f= 0.2 (n-hexane/ethyl acetate

5-Hexyl-10,20-bis(3-nitrophenyl)-15-(3,4,5-trimethoxyphenyl)-

porphyrin (79): Following general procedure C, 76 (30 mg,

0.0417 mmol), (3-nitrophenyl)boronic acid (87 mg, 0.521 mmol),

Pd(PPh₃)₄(6 mg, 0.00521 mmol), and K₃PO₄(221 mg,

1.739 mmol) in THF (50 mL) were used. Purification by column

chromatography on silica gel (n-hexane/ethyl acetate = 10:1, v/v)

followed by recrystallization from CH₂Cl₂/CH₃OH afforded the de-

sired compound (32 mg, 0.039 mmol, 96%) as purple crystals; m.p.

1

3

= 10:1, v/v). H NMR (400 MHz, CDCl₃): δ = 1.16 (t, J = 7 Hz,

3 H, CH₂CH₂CH₂CH₃), 1.86 (m, 2 H, CH₂CH₂CH₂CH₃), 2.54 (m,

3

2 H, CH₂CH₂CH₂CH₃), 4.01 (s, 6 H, OCH₃), 4.99 (t, J = 7.6 Hz,

2 H, CH₂CH₂CH₂CH₃), 7.36 (d, ³J = 8.2 Hz, 2 H, Ar-H), 7.50 (m,

3

1 H, Ar-H), 7.58 (t, J = 7.6 Hz, 2 H, Ar-H), 7.68 (t, J = 8.2 Hz,

3

2 H, Ar-H), 7.77 (s, 2 H, Ar-H), 7.82 (d, J = 7 Hz, 2 H, Ar-H),

1

8.03 (d, ³J = 7 Hz, 2 H, Ar-H), 8.99 (d, ³J = 4.7 Hz, 2 H, H_β), 9.01

Ͼ 300 °C; R_f= 0.14 (n-hexane/ethyl acetate = 10:1, v/v). H NMR

3

(400 MHz, CDCl₃): δ = –2.73 (s, 2 H, NH), 0.95 (t, J = 7 Hz, 3

(d, J = 4.7 Hz, 2 H, H_β), 9.52 (d, J = 4.7 Hz, 2 H, H_β), 9.78 (d,

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

13.7, 29.2, 35.0, 55.0, 92.0, 95.4, 98.9, 113.0, 119.8, 120.7, 126.9,

127.8, 128.2, 130.2, 131.1, 132.3, 143.4, 148.8, 149.3, 149.5, 152.0,

157.4 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 436 (4.70), 566 (3.24),

608 nm (3.33).

H, CH₂CH₂CH₂CH₂CH₂CH₃), 1.42 (m, 2 H, CH₂CH₂CH₂-

CH₂CH₂CH₃), 1.53 (m, 2 H, CH₂CH₂CH₂CH₂CH₂CH₃), 1.85 (m,

2 H, CH₂CH₂CH₂CH₂CH₂CH₃), 2.57 (m, 2 H, CH₂CH₂CH₂-

CH₂CH₂CH₃), 3.99 (s, 6 H, OCH₃), 4.19 (s, 3 H, OCH₃), 5.05 (t,

³J = 7 Hz, 2 H, CH₂CH₂CH₂CH₂CH₂CH₃), 7.46 (s, 2 H, Ar-H),

3

8.00 (t, J = 7.6 Hz, 2 H, Ar-H), 8.57 (d, J = 7.6 Hz, 2 H, Ar-H),

5-Hexyl-10,20-bis(4-methoxycarbonylphenyl)-15-(3,4,5-trimeth-

oxyphenyl)porphyrin (77): Following general procedure C, 76

(50 mg, 0.0696 mmol), (4-methoxycarbonylphenyl)boronic acid

(157 mg, 0.87 mmol), Pd(PPh₃)₄(10.1 mg, 0.0087, mmol), and

K₃PO₄(221 mg, 1.739 mmol) in THF (50 mL) were used. Purifica-

tion of the product was carried out by column chromatography

on silica gel using n-hexane/ethyl acetate (10:1, v/v) followed by

recrystallization from CH₂Cl₂/CH₃OH to give the desired com-

pound (40 mg, 0.048 mmol, 69%) as purple crystals; m.p. Ͼ

3

8.72 (m, 4 H, Ar-H), 8.84 (d, J = 4.7 Hz, 2 H, H_β), 8.98 (d, J =

4.7 Hz, 2 H, H_β), 9.10 (s, 2 H, H_β), 9.61 (d, J = 4.7 Hz, 2 H, H_β)

3

ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 13.9, 22.5, 30.0, 31.7, 35.4,

38.8, 56.2, 61.1, 116.4, 199.8, 121.8, 127.5, 128.1, 136.8, 137.8,

139.4, 143.8, 146.8 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 422

(4.97), 517 (3.76), 552 (3.43), 591 (3.33), 650 nm (3.32). HRMS

(MS ES⁺) m/z calcd. for [C₄₇H₄₃N₆O₇] [M + H⁺]: 803.3193; found

803.3204.

300 °C; R_f= 0.14 (n-hexane/ethyl acetate = 6:1, v/v). ¹H NMR

5-Hexyl-10,20-bis(4-hydroxyphenyl)-15-(3,4,5-trimethoxyphenyl)-

3

(400 MHz, CDCl₃): δ = –2.72 (s, 2 H, NH), 0.95 (t, J = 7 Hz, 3 porphyrin (80): Following general procedure C, 76 (50 mg,

H, CH₂CH₂CH₂CH₂CH₂CH₃), 1.42 (m, 2 H, CH₂CH₂CH₂- 0.0695 mmol),

(4-hydroxyphenyl)boronic

acid

(96 mg,

CH₂CH₂CH₃) 1.52 (m, 2 H, CH₂CH₂CH₂CH₂CH₂CH₃), 1.85 (m, 0.695 mmol), Pd(PPh₃)₄(8 mg, 0.00695 mmol), and K₃PO₄

2 H, CH₂CH₂CH₂CH₂CH₂CH₃), 2.65 (m, 2 H, CH₂CH₂CH₂- (295 mg, 1.39 mmol) in THF (50 mL) were used. Purification by

CH₂CH₂CH₃), 3.98 (s, 6 H, OCH₃), 4.15 (s, 3 H, OCH₃), 4.19 (s,

6 H, OCH₃), 5.05 (t, ³J = 7.6 Hz, 2 H, CH₂CH₂CH₂CH₂CH₂CH₃),

8.32 (d, ³J = 8.2 Hz, 4 H, Ar-H), 8.48 (d, ³J = 8.2 Hz, 4 H, Ar-H),

column chromatography on silica gel (CH₂Cl₂/CH₃OH = 100:1, v/

v) followed by recrystallization from CH₂Cl₂/CH₃OH gave purple

crystals (35 mg, 0.046 mmol, 67%); m.p. Ͼ 300 °C; R_f= 0.5

3

1

8.77 (d, ³J = 4.7 Hz, 2 H, H_β), 8.89 (d, J = 4.7 Hz, 2 H, H_β), 8.94

(CH₂Cl₂/CH₃OH = 100:1, v/v). H NMR (400 MHz, CDCl₃): δ =

3

(d, J = 4.7 Hz, 2 H, H_β), 9.54 (d, J = 4.7 Hz, 2 H, H_β) ppm. ¹³C

NMR (100 MHz, CDCl₃): δ = 13.5, 19.0, 24.8, 29.5, 31.7, 35.4,

52.2, 56.2, 60.1, 65.0, 112.7, 118.2, 127.0, 130.0, 147.0, 151.3,

–2.71 (s, 2 H, NH), 0.66 (t, ³J = 7 Hz, 3 H, CH₂CH₂CH₂-

CH₂CH₂CH₃), 1.41 (m, 2 H, CH₂CH₂CH₂CH₂CH₂CH₃), 1.53 (m,

2 H, CH₂CH₂CH₂CH₂CH₂CH₃), 1.84 (m, 2 H, CH₂CH₂CH₂-

5814

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Porphyrins for Use in Nonlinear Optics

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CH₂CH₂CH₃), 2.58 (m, 2 H, CH₂CH₂CH₂CH₂CH₂CH₃), 3.98 (s,

6 H, OCH₃), 4.19 (s, 3 H, OCH₃), 5.04 (t, ³J = 7.6 Hz, 2 H,

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3

2 H, Ar-H), 7.46 (s, 2 H, Ar-H), 8.09 (d, J = 8.2 Hz, 2 H, Ar-H),

[10]

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3

8.85 (d, ³J = 5.3 Hz, 2 H, H_β), 8.91 (d, J = 4.7 Hz, 2 H, H_β), 8.96

3

(d, J = 4.7 Hz, 2 H, H_β), 9.51 (d, J = 4.7 Hz, 2 H, H_β) ppm. ¹³C

NMR (100 MHz, CDCl₃): δ = 13.9, 22.7, 29.7, 31.9, 35.6, 38.9,

56.3, 61.2, 112.6, 113.4, 118.7, 119.0, 120.6, 134.8, 135.4, 137.5,

151.2, 155.2 ppm. UV/Vis (CH₂Cl₂): λ_max(logε) = 420 (4.87), 519

(4.04), 542 (3.87), 593 (3.57), 651 nm (3.53). HRMS (MS ES⁺) m/z

calcd. for [C₄₇H₄₅N₄O₅] [M + H⁺]: 745.3390; found 745.3363.

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We showed recently that the only practical way to generate

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Optical Measurements: Measurements of the optical limiting prop-

erties were carried out using the open Z-scan technique. A 6 ns Q-

switched Nd:YAG laser operating at the second harmonic of

532 nm with a pulse repetition rate of 10 Hz was used. The beam

was spatially filtered to remove the higher order modes and tightly

focused with a 9 cm focal length lens. The samples were prepared

by dissolving the porphyrin in DMF at 0.01 gL^–1followed by gen-

tle agitation for about 30 min in a low power sonic bath. All mea-

surements were performed in a quartz cell with 10 mm path length

to enhance the optical limiting response.

[14]

Acknowledgments

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This work was supported by grants from Science Foundation Ire-

land (SFI P.I. 09/IN.1/B2650) 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 measurements.

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Received: May 8, 2011

Published Online: August 24, 2011

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Article Doi

5,15-A2B2- and 5,15-A2BC-type porphyrins with donor and acceptor groups for use in nonlinear optics and photodynamic therapy

DOI: 10.1002/ejoc.201100641

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