New versatile strategy towards zinc(II)-, copper(II)- and cobalt(II)metallated thiophene/porphyrin-hybrids

Article abstract of DOI:10.1002/ejoc.200901237

A series of linear and lateral functionalised porphyrin-thiophene hybrid molecules was synthesised. Directly linked metal-free conjugates were synthesised by a successive bromination/cross-coupling sequence and transformed subsequently into zinc, copper and cobalt porphyrins. In the lateral connection mode, diverse strategies were necessary to obtain zinc and. cobalt porphyrins, whereas the synthesis of the copper derivative followed, an established route. All compounds were investigated by cyclic voltammetry. Within the series, the cobalt derivatives were exceptional because the cobalt porphyrin oxidation proved to be in competition with the thiophene oxidation. These results lead to a better understanding of the redox behaviour because such hybrid molecules consist of two independent redox centres. Furthermore, in the linear case, the absorption spectra clearly indicated an electronic influence of the thiophene periphery on the porphyrin, although conjugation is hindered strongly. 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Full text of DOI:10.1002/ejoc.200901237

FULL PAPER
DOI: 10.1002/ejoc.200901237
New Versatile Strategy towards Zinc(II)-, Copper(II)- and Cobalt(II)-
Metallated Thiophene/Porphyrin-Hybrids
Mike J. Zöllner,[a] Eike Becker,[a] Ullrich Jahn,[b] Wolfgang Kowalsky,[a] and
Hans-Hermann Johannes*[a]
Keywords: Porphyrinoids / Ligand design / Hybrid monomers / UV/Vis spectroscopy / Cyclic voltammetry
A series of linear and lateral functionalised porphyrin–thio-
phene hybrid molecules was synthesised. Directly linked
metal-free conjugates were synthesised by a successive bro-
mination/cross-coupling sequence and transformed sub-
sequently into zinc, copper and cobalt porphyrins. In the lat-
eral connection mode, diverse strategies were necessary to
obtain zinc and cobalt porphyrins, whereas the synthesis of
the copper derivative followed an established route. All com-
pounds were investigated by cyclic voltammetry. Within the
series, the cobalt derivatives were exceptional because the
cobalt porphyrin oxidation proved to be in competition with
the thiophene oxidation. These results lead to a better under-
standing of the redox behaviour because such hybrid mole-
cules consist of two independent redox centres. Furthermore,
in the linear case, the absorption spectra clearly indicated an
electronic influence of the thiophene periphery on the por-
phyrin, although conjugation is hindered strongly.
groups used varying porphyrin cores and connection pat-
terns at the meso- or β-positions of the porphyrin units,
making the comparison of the strategies difficult. A general
approach for the reliable and convenient assembly of
thiophen/porphyrin structures does not exist so far.
We recently demonstrated for nickel(II) derivatives that
the direct linear thiophene–porphyrin connection can be
easily realised using a new synthetic strategy by successive
bromination and cross-coupling reaction steps.[7] The main
advantage comes from the assembly of the free base hybrid,
which represents a good starting material for the incorpora-
tion of metals other than nickel. Here, we provide evidence
for the validity of this proposal. Furthermore, we show new
methods for the synthesis of lateral-bound copper(II),
zinc(II) and cobalt(II) porphyrin–terthiophene hybrids. All
compounds were subjected to electrochemical analysis and
are discussed in respect of their absorption properties.
Introduction
Since Heeger, Shirakawa and McDiarmid established
doped polyconjugated systems as intrinsic conducting mate-
rials in organic chemistry, researchers have studied many
systems to develop OLED, OFET, photovoltaic and sen-
soric devices.[1] In this respect, thiophene-based oligomers
and polymers proved to be very promising because a highly
diversified chemistry exists to tailor their properties.[2] Thio-
phenes are also best suited to combine electronic properties
with optical or redox properties of other functional com-
pounds, such as crown ethers, fullerenes or porphyrins.[3]
Especially, porphyrins are at the centre of interest, not only
due to their (opto-)electronic behaviour, but also due to
their metal centre, which can be modified easily.[4]
Porphyrin–thiophene hybrid systems can, in general, be
divided into lateral and linear connected types according to
Collis et al. and Wolf.[5] Representatives of the lateral type
were described by Ballarin et al., Bäuerle et al. and Collis
et al.[4d–4h,5b] Bäuerle’s and Collis’ group determined the
photovoltaic and sensoric properties of the resulting poly-
mers. Furthermore, the groups of Collis and Shimidzu de-
scribed linearly connected hybrid systems.[5b,6] However, all
Results and Discussion
Syntheses
Incorporation of diverse metal centres into the linear
thiophene–porphyrin hybrids 1, 5 and 9 was accomplished
by using the Adler–Longo method (Scheme 1).[8] The free-
base porphyrins were heated either in N,N-dimethylform-
amide (DMF) or in a mixture of MeOH, CHCl3 and tetra-
hydrofuran (THF) with the appropriate metal(II) acetate. It
was not necessary to reflux the solution because these
milder conditions of 60–80 °C proved to be better to avoid
oxidative degradation of higher oligothiophenes. The pro-
[a] Labor für Elektrooptik am Institut für Hochfrequenztechnik,
Technische Universität Braunschweig
Postfach 3329, 38023 Braunschweig, Germany
Fax: +49-531-391-8004
E-mail: h2.johannes@ihf.tu-bs.de
[b] Institute of Organic Chemistry and Biochemistry, Academy of
Sciences of the Czech Republic
Flemingovo Namesti 2, 16610 Prague, Czech Republic
E-mail: jahn@uochb.cas.cz
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.200901237.
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Metallated Thiophene/Porphyrin-Hybrids
Scheme 1. Reagents and conditions: (a) (i) Cu(OAc)2·H2O, THF/CHCl3/MeOH, reflux, 1 h, 88%; (ii) Zn(OAc)2, DMF, 60 °C, 1 h, 93 %;
(iii) Co(OAc)2·4H2O, DMF, reflux, 1 h, 79%; (iv) Cu(OAc)2·H2O, THF/CHCl3/MeOH, reflux, 1 h, 90%; (v) Zn(OAc)2, DMF, 140 °C,
1 h, 53%; (vi) Co(OAc)2·4H2O, DMF, 140 °C, 1 h, 76%; (vii) Cu(OAc)2·H2O, THF/CHCl3/MeOH, reflux, 1 h, 68%; (viii) Zn(OAc)2,
DMF, 80 °C, 1 h, 53%; (ix) Co(OAc)2·4H2O, DMF, 80 °C, 1 h, 56 %.
gress of the reaction could be monitored by thin layer uted to the high voltage conditions and resulting oxi-
chromatography (SiO2; CH2Cl2/hexane mixtures) because dations.[9] APCI-MS gave only the [M + H]+ adduct in most
the free bases gave streaky spots, whereas the metallated cases.
porphyrins were characterised by well-defined spots. For
The synthesis of laterally connected porphyrin–thio-
the thienyl 2–4 and bithienyl derivatives 6–8, average yields phene hybrids started with a regioselective Vilsmeier for-
of 80% were obtained. The terthienyls 10–12 were obtained mylation of (5,15-diphenylporphyrinato)nickel(II) at the
in somewhat lower yields of 53–68% because more exten- meso-position, according to literature, to give 13.[10] This
sive purification steps involving column chromatography reaction sequence could be adapted to the preparation of
and/or crystallisation were required. In the case of zinc por- Cu-porphyrin 14 (Scheme 2).[11] Aldehyde 14 and phos-
phyrins 3, 7 and 11, generation of the metalloporphyrins phonate 15 were subjected to a Horner–Emmons reaction
1
was confirmed by H NMR analysis, whereby the broad to give 16 in 74% yield. The configuration of the newly
signals of the tautomeric NH protons at δ = –2.6 to formed double bond could not be deduced with certainty
1
–2.8 ppm disappeared. The paramagnetic copper and co- from the H NMR spectra. However, considering the reac-
balt porphyrins 2, 4, 6, 8, 10 and 12 were identified by mass tion mechanism and the secure configuration of the analo-
spectrometry. Whereas EI mass spectrometry was the most gous nickel and zinc-compounds, it is plausible that 16 is
suitable technique for analysing the thienyl porphyrins 2–4, the E isomer. The dibromothiophene derivative 16 afforded
ESI-MS or APCI-MS were necessary to detect the higher terthiophene-connected porphyrin 18 by a Suzuki coupling
weight bisthienyl porphyrins 6–8 and terthienyl porphyrins with boronic acid 17 in 82% yield. The formation of both
10–12. Interestingly, ESI-MS produced not only the [M + copper compounds were confirmed by EI mass spectrome-
H]+ adduct ion, but also the [M]+· ion, which can be attrib- try, which showed characteristic ions of 787 [M]+·, 707
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H.-H. Johannes et al.
FULL PAPER
Scheme 2. Reagents and conditions: (a) (i) 15, NaH, DME, room temp., 22 h, 74%; (ii) 17, Pd(PPh3)4, DME, 1  Na2CO3, reflux, 3 h,
82%; (iii) concd. H2SO4/TFA, room temp., 30 min, 74%; (iv) Zn(OAc)2, DMF, reflux, 3 h, 72%; (v) 15, NaH, DME, room temp., 4 h,
70%; (vi) 17, Pd(PPh3)4, DME, 1  Na2CO3, reflux, 5 h, 64%; (vii) 15, NaH, DME, reflux.
[M+·– Br] and 627 [M+· – 2 Br] for 16, and 995 [M]+· for Horner–Emmons reactions presented here, in this case the
18.
solution required heating to reflux. This can be rationalised
Because zinc porphyrin 20 was not available through di- on the basis that the free base macrocycle is more electron-
rect formylation of (5,15-diphenylporphyrinato)zinc(II), its poor compared to the dianionic species of metallated por-
synthesis therefore started with the demetallation of 13 un- phyrins. The following Suzuki coupling proceeded unevent-
der acidic conditions.[11,12] The metal-free porphyrincarb- fully to give terthiophene 24 in 82% yield. For insertion of
aldehyde 19 was obtained in 74% yield. Subsequent zinc the metal, 24 was heated to reflux with cobalt(II) acetate in
incorporation into 19 furnished 20 in 72% yield.[13] The ter- DMF, according to the general Adler–Longo procedure.[8]
thiophene 22 was prepared similarly by a Horner–Emmons The thiophene–porphyrin hybrid 25 was obtained in 61%
reaction, which gave 70% of 21, and a subsequent Suzuki yield and characterised by the high intensity ions of 991
coupling in 64% yield. The formation of the E isomer was [M]+· in the ESI-MS and 992 [M + H]+ in the APCI-MS.
verified for both 21 and 22 by the coupling constants of J
= 16.0 Hz and J = 15.8 Hz, respectively, for the vinylene
protons.
Absorption Spectra
The corresponding cobalt derivative is expected to be
sensitive to oxidation and therefore difficult to purify by
For all target compounds, the absorption spectra showed
column chromatography. To circumvent these problems, a the typical bands for metallated porphyrins Ϫ one Soret
synthetic route involving the free base with incorporation band and two Q bands Ϫ that were indicative for successful
of the cobalt as the last step was envisaged because the me- metal insertion into the free base porphyrins.[14] Comparing
tallation process can often be performed without the members with increasing thiophene chain lengths (2/6/
chromatography. A Horner–Emmons reaction with por- 10, 3/7/11 and 4/8/12) within the linear connected thio-
phyrin 19 and phosphonate 17 yielded 60% of 23 as the phene–porphyrin hybrids series provided interesting results.
pure E isomer (J = 16.0 Hz). In contrast to the all other For all the metal cores, not only did the α-band shift to the
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Metallated Thiophene/Porphyrin-Hybrids
Figure 1. Absorption spectra of all linearly connected thiophene/porphyrin hybrids.
red due to the extension of the π-system, but the Soret band electron-donating effect from the thiophene periphery
also broadened significantly without shifting its position towards the porphyrin can thus be drawn. This is more re-
(full width at half maximum, fwhm). At 10–20% of the markable if one considers that conjugation between both
maximum, this tendency was even more prominent. aromatic systems is hindered due to steric repulsion.[17]
A
Furthermore, for the zinc and copper derivatives, the further hint supporting this conclusion was found in the
α-band intensity was raised compared to the β-band broadened Soret band. The groups of Wolf, Röder and
(Figure 1). Table 1 summarises all significant data.
Odobel made similar observations concerning the Soret
band and traced it back to the donating properties of the
peripheral thiophene unit;[4j–4l,18] Rochford et al. describe
similar effects for meso-substituted thien-2-ylzinc por-
phyrins.[19] Nonetheless, until now it has not been clear
whether this effect is based on minimal conjugation or con-
jugation-independent redox processes, for example on a
through-bond super-exchange mechanism.
Table 1. Details of the Soret-, α- and β-bands.
Compound Metal
Soret band fwhm
Absorption
α/β
[nm]
[nm]
CuDPP[a]
Cu
Zn
Co
403
418
417
418
11
15
35
40
1:3.6
1:3.9
1:2.0
1:1.5
2
6
10
ZnDPP[a]
3
7
11
CoDPP[a]
4
8
12
407
422
423
425
11
15
34
37
1:7.8
1:3.5
1:1.5
1:1.1
Cyclic Voltammetry
Electropolymerisation offers many advantages compared
to chemical polymerisation methods.[1b,20] When the re-
sulting polymer is not soluble in organic solvents its pro-
cessing may become difficult and, for such cases, electropo-
lymerisation raises the possibility of depositing the polymer
onto structured electrodes directly. Due to the anodic poly-
merisation mechanism, knowledge about the oxidation pro-
cesses is fundamental and, in this respect, cyclic voltamme-
try is indispensable. Thereby, cyclic voltammetry experi-
ments of linearly bound porphyrins gave interesting results
(Figure 2). When the thiophene periphery was elongated
from thienyl to terthiophenyl, the first oxidation peak,
which was irreversible, shifted to lower potentials for the
copper (2, 6 and 10) and zinc (3, 7 and 11) derivatives. The
oxidation peaks were located at 1.12–1.19 V for the thio-
phene periphery, at 1.04–1.09 V for the bithiophenyls and
at 0.86–0.88 V for the terthiophenyls. These results are in
good agreement with the oxidation potentials reported for
398
414
415
417
17
25
53
53
1:1.8
1:1.5
1:1.8
1:1.7
[a] DPP = 5,15-diphenylporphyrin; the metallated porphyrins were
used as references.
These observations can be explained by taking the
Gouterman-Four-Orbital-Theory into account.[14] Gouter-
man describes two degenerated LUMOs, eg, and two almost
degenerate frontier orbitals, A1u and A2u; significantly,
whereas the former frontier orbital includes a nodal plane
at the meso-position, the second does not. Therefore, elec-
tron-donating effects would affect the A2u orbital in particu-
lar. With regard to the correlation
Aα/Aβ ≈ [∆E(A2u, eg) – ∆E(A1u, eg)]2
and provided that for 10,20-arylated 5,15-diphenylpor- the analogous nickel complexes.[7] The first oxidation po-
phyrins the difference ∆E(A2u, eg) – ∆E(A1u, eg) is negative, tential of the linearly connected cobalt porphyrins (4 and
this means that electron-donating groups connected at the 8: 0.96 V) did not change for the thienyls and bithiophenyls.
meso-position will raise the A2u orbital, reduce the ∆E- Furthermore, it showed reversible character, especially
(A2u, eg) and therefore increase the α-band intensity.[15] Ac- when the vertex potentials were reduced to lower values (see
tually, the difference is described as negative for 5,10,15,20- the Supporting Information for further CV experiments
tetraphenylporphyrins.[15,16] The conclusion that there is an with 4, 8 and 12). An approximation to the cyclic voltam-
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H.-H. Johannes et al.
FULL PAPER
Figure 2. Cyclic voltammograms of the linearly connected thiophene/porphyrin hybrids.
Figure 3. Cyclic voltammograms of the laterally connected thiophene/porphyrin hybrids.
metry behaviour of the other porphyrin complexes was not very comprehensive review on the electrochemistry of
observed until the oligothiophene chain was a terthiophene metalloporhyrins.[21]
(12). In this case the first oxidation wave was a double
An exceptional role for cobalt porphyrins was even found
peaked signal with two maxima at 0.83 V and 0.93 V. The in the lateral case (Figure 3). The copper and zinc com-
former peak corresponded to those of 10 and 11 and the plexes 18 and 21 showed the same irreversible first oxi-
latter can be attributed to a cobalt porphyrin oxidation pro- dation occurring at 0.96 V, which was comparable to that
cess. The fact that the oxidation events of copper- and zinc- of the reported nickel derivative.[7] In contrast, cobalt por-
containing hybrids are fundamentally different to those of phyrin 25 was oxidised at a lower potential of 0.85 V; com-
cobalt can be explained by comparison with the cyclic vol- pared to 12, this was slightly shifted to lower potentials due
tammograms of the analogous 5,15-diphenylporphyrins to the electron-donating effect of the vinyl-bonded terthi-
(DPP; see the Supporting Information). CoDPP has the ophene unit. The reversibility of the first oxidation event of
lowest oxidation potential among them. Because the lin- 25 became clear when the vertex potentials were reduced to
early connected thiophene–porphyrin hybrids consist of two lower values (Figure 3, insets).
almost independent redox units, the thiophene and por-
phyrin oxidations occur according to their ease of oxi-
dation.[7] The irreversible thiophene oxidation is the first to
occur in the case of copper and zinc porphyrins. For the
Conclusions
cobalt complexes, the reversible cobalt porphyrin is most
The results presented here show that the electrooxidation
sensitive to oxidation. Only in the trishexoxyterthiophene- of thiophene–porphyrin hybrid systems is regiodefined and
carrying cobalt complex is the thiophene unit more easily that the overall oxidation process is dependent on the be-
oxidised. The assignment of the peak at 0.93 V as an oxi- haviour of the individual units. For electropolymerisation,
dation process at the cobalt porphyrin unit is strengthened the following facts must be considered: Cobalt porphyrins
by its reversible character, because irreversible electropo- differ especially from analogous nickel, copper and zinc
lymerisation processes should occur when the thiophene complexes due to their low oxidation potential, which com-
was oxidised.[20f,20g] Whether the first cobalt porphyrin oxi- petes with the thiophene oxidation in most cases. For lin-
dation takes place at the π-system of the porphyrin or at is early connected thiophene–porphyrin units, a small degree
metal-centre is not yet clear. Kadish describes both in his of electronic communication between the thiophene and
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Metallated Thiophene/Porphyrin-Hybrids
the reaction was complete the solution was cooled to r.t. and
CH2Cl2 was added. Washing the organic phase and drying over
MgSO4 gave the product after crystallisation from CH2Cl2/MeOH
or flash column chromatography.
porphyrin units can be assumed. Thiophene acts as an elec-
tron donor, resulting in a remarkable broadening of the So-
ret band of the porphyrin and an increase in the α-band
intensity. Only for cobalt complexes does the α-band seem
to be unaffected, which underlines their exceptional role in
the investigated series.
General Procedure for Horner–Emmons Reaction. Method II: The
aldehyde and the phosphonate 15 were dissolved in DME. NaH
(60% in mineral oil) was added at r.t. and the mixture was stirred.
After reaction (completion was indicated by TLC), water was
added and the mixture was extracted with CH2Cl2. The combined
organic phases were dried with MgSO4, the solvents removed and
the crude product was purified by flash column chromatography.
Experimental Section
General: Air- and moisture-sensitive reactions were carried out un-
der nitrogen in flame-dried flasks. Anhydrous solvents were used
as received. Reaction progress was monitored by thin layer
chromatography on Polygram SIL G/UV254 plates (Macherey–
Nagel). Silica gel 60M (Macherey–Nagel) was used for column
chromatographic separations. Melting points were determined with
a Stuart-Melting-Point SMP3 or by DSC measurements (Mettler
DSC 20) taking peak onsets. NMR spectra were obtained
with Bruker DRX 400 (1H: NMR 400.14 MHz; 13C: NMR
100.62 MHz) or Bruker Avance 2 (1H: NMR 600.13 MHz; 13C:
NMR 150.90 MHz) spectrometers; the samples were measured as
CDCl3 solutions. 1H NMR chemical shifts (δ) are given in ppm
relative to TMS as internal standard, 13C shifts relative to CDCl3
(δ = 77.3 ppm). Data are reported as follows: s = singlet, d = doub-
let, dd = doublet of doublet, t = triplet. Free base porphyrins
showed the α- and β-carbon signals of the pyrrole unit merging
into one broad signal because of the tautomeric NH protons.[22]
Appellation of the hydrogen and carbon atoms is defined in the
Supporting Information. Mass spectra measurements (EI and ESI)
were performed at the Institut für Organische Chemie, Technische
Universität Braunschweig with a MAT 95 (Thermofinnigan) in-
strument; Low-resolution EI (electron ionisation at 70 eV), or high-
resolution EI with peak matching method at a resolution of 10000
with PFK as mass calibrant. ESI mass spectra were obtained with
a MAT 95XLT (Thermofinnigan) instrument. Concentrations were
approx. 50 µL/mL, solvents are noted in the analytical section.
Spray voltages in positive mode were 1.3–1.8 kV. APCI high-resolu-
tion mass spectra were recorded at the IOCB AS, Prague with a
LTQ Orbitrap XL (Thermo Fisher Scientific) instrument, low-reso-
lution spectra with a LC Fleet (Thermo Fisher Scientific) instru-
ment. UV/Vis and IR spectra were recorded with Carry 100 Bio
(Varian) and ATR Diamond Tensor 27 (Bruker) spectrometers. IR
bands are characterised by intensity: w = weak, m = medium, s
= strong. Elemental analyses were performed at the Institut für
Pharmazeutische Chemie, Technische Universität Braunschweig.
Cyclic voltammetry was performed with a Metrohm µAutolab in-
strument equipped with a 1-mm platin disc working electrode, a
platin wire counter electrode and a saturated Ag/AgCl reference
electrode. The electrolyte Bu4NPF6 was dissolved in anhydrous
dichloromethane, which was stored under a nitrogen atmosphere,
to generate a 0.1  oxygen-free stock solution. Monomer concen-
trations were set to 0.1 m. Scan rate was set to 100 mV/s. The
ferrocene/ferrocenium redox couple was determined at 0.65 V.
Compounds 1,[7] 5,[7] 9,[7] 13,[10] 14,[11] 15,[23] 17,[24] 19[11,12] and
20[13] were synthesised according to literature procedures.
General Procedure for Suzuki Coupling. Method III: A solution of
the corresponding 2,5-bromothiophene, Pd(PPh3)4, boronic acid
17, aqueous Na2CO3 solution and either DME or DMF was heated
to reflux and rigorously stirred. After the reaction was complete
(indicated by TLC), the reaction mixture was cooled to room temp.
and water was added. The mixture was extracted and the combined
organic phases were dried with MgSO4. Removing the solvents and
purification of the crude product by crystallisation or flash column
chromatography gave the desired product.
{5,15-Bis[4-(hexoxy)thien-2-yl]-10,20-diphenylporphyrinato}-
copper(II) (2): (Method IB) Compound 1 (200 mg, 242 µmol),
Cu(OAc)2·H2O (242 mg, 1.21 mmol), MeOH (5 mL), THF
(10 mL), CHCl3 (10 mL), 1 h reflux, adding CH2Cl2 (30 mL),
washing with aqueous saturated NH4Cl (30 mL) and H2O
(2ϫ 30 mL), and recrystallisation from CH2Cl2/MeOH (30 mL/
5 mL) gave 2 (190 mg, 214 µmol, 88%); purple crystals; m.p. 207 °C
(DSC peak onset). MS (EI): m/z (%) = 887/888/889/890/891/892
(100/58/69/33/13) [M]+·. HRMS (EI): calcd. for C52H48CuN4O2S2
[M]+· 887.2515; found 887.2480. FTIR: ν = 3110 (w), 3049 (w),
˜
2923 (w), 2856 (w), 1555 (w), 1512 (w), 1458 (m), 1440 (w), 1359
(m), 1208 (w), 1166 (s), 1072 (m), 1048 (w), 1029 (w), 1001 (s), 969
(m), 872 (w), 812 (m), 792 (s), 754 (m), 700 (m) cm–1. UV/Vis: λ
(ε) = 575 (6200), 541 (21200), 418 (381600) nm. C52H48CuN4O2S2
(888.64): calcd. C 70.28, H 5.44, N 6.30, S 7.22; found C 70.02, H
5.48, N 6.55, S 6.68.
{5,15-Bis[4-(hexoxy)thien-2-yl]-10,20-diphenylporphyrinato}zinc(II)
(3): (Method IA) Compound 1 (400 mg, 484 µmol), Zn(OAc)2
(1000 mg, 6.44 mmol), DMF (20 mL), 1 h at 80 °C, adding H2O
(100 mL), and two times recrystallisation from CH2Cl2/MeOH
(40 mL/10 mL) gave 3 (400 mg, 449 µmol, 93%); purple crystals;
1
m.p. 184 °C (DSC peak onset). H NMR (600 MHz): δ = 9.23 (d,
3
3J8,7 = 4.6 Hz, 4 H, 8-H), 8.93 (d, J7,8 = 4.6 Hz, 4 H, 7-H), 8.22–
4
8.18 (m, 4 H, 3-H), 7.79–7.72 (m, 6 H, 1,2-H), 7.60 (d, J12,14
=
4
1.8 Hz, 2 H, 12-H), 6.70 (d, J14,12 = 1.8 Hz, 2 H, 14-H), 4.18 (t,
3J15,16 = 6.7 Hz, 4 H, 15-H), 1.93–1.87 (m, 4 H, 16-H), 1.59–1.53
3
(m, 4 H, 17-H), 1.45–1.36 (m, 8 H, 18,19-H), 0.94 (t, J20,19
=
7.1 Hz, 6 H, 20-H) ppm. 13C NMR (150 MHz): δ = 156.0 (s, C-
13), 150.7 (s, C-9), 150.5 (s, C-6), 142.6 (s, C-4), 142.5 (s, C-11),
134.4 (d, C-3), 132.2 (d, C-7), 131.9 (d, C-8), 127.6 (d, C-1), 126.6
(d, C-2), 126.3 (d, C-12), 121.8 (s, C-5), 112.8 (s, C-10), 99.8 (d, C-
14), 70.3 (t, C-15), 31.7 (t, C-18), 29.4 (t, C-16), 25.9 (t, C-17), 22.7
(t, C-19), 14.1 (q, C-20) ppm. MS (EI): m/z (%) = 888/889/890/891/
892/893 (100/54/75/48/54/26/10) [M]+·. HRMS (EI): calcd. for
General Procedure for Metal Insertion. Method IA: The free base
porphyrin and the metal acetate were heated in DMF. After the
reaction was complete, water was added and the precipitate was
filtered off and washed. The solid was either crystallised from
CH2Cl2/MeOH or purified by flash column chromatography.
C52H48N4O2S2Zn [M]+· 888.2510; found 888.2497. FTIR: ν = 3109
˜
(w), 2925 (w), 2853 (w), 1552 (w), 1496 (w), 1456 (w), 1362 (m),
1336 (m), 1208 (w), 1164 (m), 1070 (w), 1022 (m), 989 (m), 969
(m), 871 (w), 823 (w), 809 (w), 793 (s), 744 (m), 717 (m), 702 (s)
cm–1. UV/Vis: λ (ε) = 592 (5600), 550 (19600), 422 (400000) nm.
C52H48N4O2S2Zn (890.50): calcd. C 70.14, H 5.43, N 6.29, S 7.20;
found C 69.33, H 5.52, N 6.27, S 6.89.
Method IB: The free base porphyrin and the metal acetate were
heated in either DMF or a mixture of THF/CHCl3/MeOH. After
Eur. J. Org. Chem. 2010, 4426–4435
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4431

H.-H. Johannes et al.
FULL PAPER
{5,15-Bis[4-(hexoxy)thien-2-yl]-10,20-diphenylporphyrinato}-
cobalt(II) (4): (Method IB) Compound 1 (200 mg, 242 µmol),
Co(OAc)2·4H2O (850 mg, 3.41 mmol), DMF (15 mL), 1 h reflux,
adding CH2Cl2 (50 mL), washing with H2O (5ϫ50 mL), and two
times recrystallisation from CH2Cl2/MeOH (20 mL/5 mL) gave 4
(170 mg, 192 µmol, 79%); red-brownish solid; m.p. 177 °C (DSC
peak onset). MS (EI): m/z (%) = 883/884/885 (100/53/27) [M]+·.
HRMS (EI): calcd. for C52H48CoN4O2S2 [M]+· 883.2551; found
{5,15-Bis[3,4Ј-bis(hexoxy)-2,2Ј-bithiophen-5-yl]-10,20-diphenylpor-
phyrinato}cobalt(II) (8): (Method IB) Compound 5 (250 mg,
210 µmol), Co(OAc)2·4H2O (600 mg, 2.41 mmol), DMF (15 mL),
1 h 140 °C, addition of CH2Cl2 (100 mL), washing with saturated
aqueous NH4Cl (3ϫ50 mL), H2O (50 mL) and brine (50 mL), and
removal of solvents gave 8 (200 mg, 160 µmol, 76%); purple solid;
m.p. 104 °C (DSC peak onset). MS (ESI MeOH): m/z (%) = 1247/
1248/1249/1250 (100/86/54/27) [M+·/M + H+]. MS (APCI, CHCl3):
883.2533. FTIR: ν = 2952 (w), 2927 (w), 2856 (w), 1557 (w), 1536 m/z (%) = 1247/1248/1249/1250 (57/100/59/49) [M+·/M + H+].
˜
(w), 1462 (w), 1442 (w), 1363 (m), 1167 (s), 1068 (m), 1003 (m), HRMS (APCI, CHCl3): calcd. for C72H77CoN4O4S4 [M + H+]
974 (m), 814 (m), 791 (s), 747 (m), 715 (m) cm–1. UV/Vis: λ (ε) =
559 (sh.), 533 (15000), 414 (195700) nm. C52H48CoN4O2S2
(884.03): calcd. C 70.65, H 5.47, N 6.34, S 7.25; found C 70.44, H
5.48, N 6.52, S 6.98.
1248.4154; found 1248.4126. FTIR: ν = 3119 (w), 3056 (w), 2925
˜
(m), 2855 (m), 1566 (m), 1541 (m), 1459 (m), 1399 (w), 1353 (s),
1167 (m), 1073 (m), 1002 (s), 985 (m), 863 (w), 792 (s), 751 (m)
cm–1. UV/Vis: λ (ε) = 575 (sh.), 535 (17200), 415 (135900) nm.
C72H76CoN4O4S4 (1248.59): calcd. C 69.26, H 6.14, N 4.49, S
10.27; found C 69.17, H 6.13, N 4.61, S 9.70.
{5,15-Bis[3,4Ј-bis(hexoxy)-2,2Ј-bithiophen-5-yl]-10,20-diphenylpor-
phyrinato}copper(II) (6): (Method IB) Compound 5 (210 mg,
176 µmol), Cu(OAc)2·H2O (170 mg, 851 µmol), MeOH (5 mL),
THF (10 mL), CHCl3 (10 mL), 1 h reflux, washing with H2O
(2ϫ50 mL), and recrystallisation from CH2Cl2/MeOH (30 mL/
10 mL) gave 6 (200 mg, 160 µmol, 90 %); purple crystals; m.p.
170 °C (DSC peak onset). MS (ESI MeOH): (%) m/z = 1251/1252/
1253/1254/1255/1256 (75/92/100/76/47/15) [M+·/M + H+]. MS
(APCI, CHCl3): m/z (%) = 1252/1253/1254/1255/1256/1257 (39/100/
84/59/24/22) [M + H+]. HRMS (APCI, CHCl3): calcd. for
{5,15-Bis[3,3Ј,4ЈЈ-tris(hexoxy)-2,5Ј:2Ј,2ЈЈ-terthiophen-5-yl]-10,20-
diphenylporphyrinato}copper(II) (10): (Method IB) Compound 9
(160 mg, 105 µmol), Cu(OAc)2·H2O (130 mg, 650 µmol), MeOH
(2.5 mL), THF (5 mL), CHCl3 (5 mL), 1 h reflux, cooling to r.t.
and removing the solvents gave the crude product that was purified
by flash chromatography (hexane/CH2Cl2, 3:2, Rf = 0.46) to give
10 (100 mg, 62 µmol, 60%); purple solid; m.p. Ͼ 250 °C (decomp.).
MS (ESI ACN/Toluene): m/z (%) = 1616/1617/1618/1619/1620/
1621/1622/1623 (7/76/85/100/77/81/29/17) [M+·/M + H+].
MS (APCI, CHCl3): m/z (%) = 1617/1618/1619/1620/1621/1622 (86/
100/98/74/48/24) [M + H+]. HRMS (APCI, CHCl3): calcd. for
C92H105CuN4O6S6 [M + H+] 1616.5654; found 1616.5633. FTIR:
C H CuN O S [M + H+] 1252.4118; found 1252.4095. FTIR: ν
˜
72 77
4
4 4
= 3108 (w), 3056 (w), 3025 (w), 2925 (m), 2857 (m), 1544 (m), 1520
(w), 1463 (w), 1347 (s), 1311 (w), 1206 (w), 1168 (s), 1123 (w), 1072
(m), 997 (s), 976 (m), 926 (w), 904 (w), 864 (w), 816 (m), 796 (s),
749 (m), 717 (m) cm–1. UV/V: λ (ε) = 591 (10500), 546 (21600), 417
(202000) nm. C72H76CuN4O4S4 (1253.2): calcd. C 69.00, H 6.11, N
4.47, S 10.23; found C 68.60, H 5.99, N 4.58, S 10.02.
ν = 3110 (w), 3056 (w), 2925 (m), 2855 (m), 1569 (m), 1536 (m),
˜
1455 (m), 1403 (w), 1349 (s), 1168 (m), 1071 (s), 1001 (s), 977 (m),
793 (s), 752 (m), 716 (m) cm–1. UV/Vis: λ (ε) = 598 (17400), 547
(25900), 418 (226300) nm. C92H104CuN4O6S6 (1617.77): calcd. C
68.30, H 6.48, N 3.46, S 11.89; found C 68.66, H 6.60, N 3.62, S
11.46.
{5,15-Bis[3,4Ј-bis(hexoxy)-2,2Ј-bithiophen-5-yl]-10,20-diphenyl-
porphyrinato}zinc(II) (7): (Method IA) Compound 5 (230 mg,
242 µmol), Zn(OAc)2 (370 mg, 2.02 mmol), DMF (10 mL), 1 h at
140 °C, addition of H2O (50 mL), washing with H2O and MeOH,
and flash chromatography (hexane/CH2Cl2, 1:1, Rf = 0.46) gave 7
(310 mg, 104 µmol, 53%); purple solid; m.p. Ͼ 230 °C (decomp.).
{5,15-Bis[3,3Ј,4ЈЈ-tris(hexoxy)-2,5Ј:2Ј,2ЈЈ-terthiophen-5-yl]-10,20-
diphenylporphyrinato}zinc(II) (11): (Method IA) Compound 9
(290 mg, 186 µmol), Zn(OAc)2 (370 mg, 2.02 mmol), DMF
(10 mL), 1 h at 80 °C, adding H2O (50 mL), and two times flash
chromatography (hexane/CH2Cl2, 1:1, Rf = 0.54) gave 11 (160 mg,
3
1H NMR (600 MHz): δ = 9.31 (d, J = 4.6 Hz, 4 H, 8-H), 8.96 (d,
3J = 4.6 Hz, 4 H, 7-H), 8.23–8.18 (m, 4 H, 3-H), 7.81–7.73 (m, 6 H, 99 µmol, 53 %); purple solid; m.p. 92 °C (DSC peak onset). 1H
4
3
1,2-H), 7.67 (s, 2 H, 12-H), 7.01 (d, J = 1.5 Hz, 2 H, 22-H), 6.14
NMR (600 MHz): δ = 9.32 (d, J8,7 = 4.6 Hz, 4 H, 8-H), 8.96 (d,
4
3
(d, J = 1.5 Hz, 2 H, 24-H), 4.31 (d, J = 6.5 Hz, 4 H, 25-H), 3.91
3J7,8 = 4.6 Hz, 4 H, 7-H), 8.23–8.19 (m, 4 H, 3-H), 7.79–7.72 (m,
(d, 3J = 6.5 Hz, 4 H, 25-H), 1.99–1.93 (m, 4 H, 16-H), 1.77–1.71
6 H, 1,2-H), 7.64 (s, 2 H, 12-H), 6.90 (s, 2 H, 22-H), 6.73 (d, 4J32,34
4
(m, 4 H, 26-H), 1.64–1.57 (m, 4 H, 17-H), 1.46–1.29 (m, 20 H, = 1.7 Hz, 2 H, 32-H), 5.99 (d, J34,32 = 1.7 Hz, 2 H, 34-H), 4.29 (t,
18,19,27,28,29-H), 0.96–0.87 (m, 12 H, 20,30-H) ppm. 13C NMR 3J15,16 = 6.4 Hz, 4 H, 15-H), 3.88 (t, J25,26 = 6.6 Hz, 4 H, 25-H),
3
3
(150 MHz): δ = 157.1 (s, C-23), 151.6 (s, C-13), 150.7 (s, C-9), 150.5
(s, C-6), 142.5 (s, C-4), 139.1 (s, C-11), 134.4 (d, C-3), 133.6 (s, C-
21), 132.5 (d, C-7), 131.8 (d, C-8), 127.7 (d, C-1), 126.6 (d, C-2),
124.3 (d, C-12), 122.0 (s, C-5), 118.3 (s, C-14), 114.5 (d, C-22),
112.4 (s, C-10), 95.8 (d, C-24), 72.2 (t, C-15), 70.1 (t, C-25), 31.60
(t, C-18,28), 29.7 (t, C-16), 29.2 (t, C-26), 25.8 (t, C-17), 25.7 (t, C-
3.85 (t, J35,36 = 6.6 Hz, 4 H, 35-H), 1.98–1.90 (m, 4 H, 16-H),
1.75–1.59 (m, 12 H, 36,26,17-H), 1.46–1.26 (m, 32 H, 27,37,18,
3
28,38,19,29,39-H), 0.94 (t, J = 7.1 Hz, 6 H, 20/30/40-H), 0.91 (t,
3
3J = 7.1 Hz, 6 H, 20/30/40-H), 0.88 (t, J = 7.0 Hz, 6 H, 20/30/40-
H) ppm. 13C NMR (150 MHz): δ = 157.0 (s, C-33), 152.3 (s, C-23),
151.9 (s, C-13), 150.7 (s, C-9), 150.6 (s, C-6), 142.5 (s, C-4), 139.3
27), 22.63 (t, C-19), 22.62 (t, C-29), 14.09 (q, C-20), 14.08 (q, C- (s, C-11), 134.5 (d, C-3), 133.9 (s, C-31), 132.5 (d, C-7), 131.8 (d,
30) ppm. MS (ESI MeOH): m/z (%) = 1252/1253/1254/1255/1256/
1257/1258/1259 (57/96/100/91/97/ 68/42/17) [M+·/M + H+]. MS
(APCI, CHCl3): m/z (%) = 1253/1254/1255/1256/1257/1258/1259
(67/100/77/61/ 75/36/22) [M + H+]. HRMS (APCI, CHCl3): calcd.
for C72H77ZnN4O4S4 [M + H+] 1253.4114; found 1253.4093. FTIR:
C-8), 130.5 (s, C-21), 127.6 (d, C-1), 126.6 (d, C-2), 124.3 (d, C-
12), 122.1 (s, C-5), 118.4 (s, C-14), 113.74 (d, C-32), 113.70 (s, C-
24), 112.3 (s, C-10), 112.0 (d, C-22), 95.2 (d, C-34), 72.3 (t, C-15),
71.7 (t, C-25), 70.0 (t, C-35), 31.64 (t, C-18/28/38), 31.61 (t, C-18/
28/38), 31.5 (t, C-18/28/38), 29.7 (t, C-16), 29.4 (t, C-26), 29.2 (t,
ν = 3109 (w), 3054 (w), 2950 (m), 2924 (m), 2854 (m), 1569 (m), C-36), 25.9 (t, C-17/27/37), 25.7 (t, C-17/27/37), 25.6 (t, C-17/27/
˜
1540 (m), 1497 (w), 1462 (w), 1439 (w), 1397 (w), 1356 (m), 1206 37), 22.7 (t, C-19/29/39), 22.63 (t, C-19/29/39), 22.57 (t, C-19/29/
(w), 1167 (m), 1069 (m), 993 (s), 974 (m), 863 (w), 791 (s), 751
39), 14.12 (q, C-20/30/40), 14.08 (q, C-20/30/40), 14.04 (q, C-20/30/
40) ppm. MS (ESI ACN/Toluene): m/z (%) = 1617/1618/1619/1620/
(w), 717 (m) cm–1. UV/Vis: λ (ε) = 603 (13200), 554 (20400), 423
(212900) nm. C72H76N4O4S4Zn (1255.07): calcd. C 68.90, H 6.10, 1621/1622/1623/1624/1625 (39/79/95/100/94/84/63/43/28) [M+·/M +
N 4.46, S 10.22; found C 68.98, H 6.18, N 4.45, S 9.79.
H+]. MS (APCI, CHCl3): m/z (%) = 1618/1619/1620/1621/1622/
4432
www.eurjoc.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 4426–4435

Metallated Thiophene/Porphyrin-Hybrids
1623/1624/1625 (68/80/100/78/88/56/42/20) [M + H+]. HRMS {10-[2-(2,5-Dibromothien-3-yl)vinyl]-5,15-diphenylporphyrinato}-
(APCI, CHCl3): calcd. for C92H105N4O6S6Zn [M + H+] 1617.5650; zinc(II) (21): (Method II) Compound 20 (260 mg, 470 µmol), 15
found 1617.5624. FTIR: ν = 3112 (w), 3055 (w), 2924 (m), 2854
(202 mg, 534 µmol), DME (7 mL), NaH (60 % in mineral oil,
˜
(m), 1569 (m), 1535 (m), 1457 (m), 1439 (w), 1401 (w), 1352 (s),
73 mg, 1.75 mmol), 4 h at r.t., adding H2O (20 mL), extraction with
1207 (m), 1168 (m), 1070 (s), 997 (m), 974 (m), 907 (w), 792 (s), CH2Cl2 (3ϫ60 mL), washing with brine (50 mL), and purification
752 (w), 718 (m) cm–1. UV/Vis: λ (ε) = 613 (21200), 555 (23600),
by flash chromatography (CH2Cl2; Rf = 0.95) gave 21 (275 mg,
425 (228400) nm. C92H104N4O6S6Zn (1619.63): calcd. C 68.22, H 347 µmol, 70%); purple solid; m.p. Ͼ290 °C. 1H NMR (600 MHz):
6.47, N 3.46, S 11.88; found C 67.96, H 6.45, N 3.66, S 11.73.
δ = 10.07 (s, 1 H, 15-H), 9.45 (d, 3J8,7 = 4.6 Hz, 2 H, 8-H), 9.42 (d,
3J16,17 = 16.0 Hz, 1 H, 16-H), 9.27 (d, 3J13,12 = 4.4 Hz, 2 H, 13-H),
{5,15-Bis[3,3Ј,4ЈЈ-tris(hexoxy)-2,5Ј:2Ј,2ЈЈ-terthiophen-5-yl]-10,20-
diphenylporphyrinato}cobalt(II) (12): (Method IA) Compound 9
(150 mg, 96 µmol), Co(OAc)2·4H2O (400 mg, 1.61 mmol), DMF
(7.5 mL), 1 h, 80 °C, adding H2O (50 mL), washing with H2O and
MeOH. The solid was recrystalised from MeOH/CH2Cl2 (5 mL/
15 mL) and the methanol phase was cooled to –18 °C for some
days. The precipitated solid was filtered off to give 12 (86 mg,
53 µmol, 56%); purple solid; m.p. Ͼ 240 °C (decomp.). MS (ESI
ACN/Toluene): m/z (%) = 1612/1613/1614/1615/1616/1617 (78/100/
87/57/32/16) [M+·/M + H+]. MS (APCI, CHCl3): m/z (%) = 1613/
1614/1615/1616/1617 (100/98/76/40/22) [M + H+]. HRMS (APCI,
CHCl3): calcd. for C92H105CoN4O6S6 [M + H+] 1612.5690; found
3
3
9.00 (d, J12,13 = 4.4 Hz, 2 H, 12-H), 8.98 (d, J7,8 = 4.6 Hz, 2 H,
7-H), 8.21–8.18 (m, 4 H, 3-H), 7.83–7.76 (m, 6 H, 1,2-H), 7.81 (s,
1 H, 20-H), 7.22 (d, J17,16 = 16.0 Hz, 1 H, 17-H) ppm. 13C NMR
3
(150 MHz): δ = 150.0 (s, C-11), 149.8 (s, C-14), 149.7 (s, C-6), 148.6
(s, C-9), 142.5 (s, C-4), 140.0 (s, C-19), 134.5 (d, C-3), 133.3 (d, C-
17), 132.6 (d, C-12), 132.4 (d, C-16), 132.1 (d, C-7), 131.7 (d, C-
13), 129.7 (d, C-8), 127.7 (d, C-20), 127.5 (d, C-1), 126.6 (d, C-2),
120.8 (s, C-5), 116.7 (s, C-10), 112.3 (s, C-21), 111.2 (s, C-18), 106.0
(s, C-15) ppm. MS (ESI MeOH/CHCl3): m/z (%) = 788/789/790/
791/792/793/794/795/796 (38/17/93/47/100/52/62/26/25) [M+·/M +
H+]. MS (APCI, MeOH/CHCl3): m/z = 788/789/790/791/792/793/
794/795/796 (38/24/81/48/ 100/57/60/35/20) [M+·/M+H+]. HRMS
1612.5671. FTIR: ν = 3112 (w), 3056 (w), 2926 (m), 2856 (m), 1569
˜
(APCI, MeOH/CHCl3): calcd. for C38H22Br2N4SZn [M+·
]
(m), 1536 (m), 1455 (m), 1403 (w), 1353 (s), 1169 (m), 1073 (s),
1003 (m), 984 (m), 905 (w), 793 (s), 751 (m), 715 (m) cm–1. UV/
Vis: λ (ε) = 585 (10900), 537 (19000), 417 (157800) nm.
787.9218; found 787.9223. FTIR: ν = 3044 (w), 1593 (w), 1519 (w),
˜
1486 (w), 1437 (w), 1420 (w), 1383 (w), 1318 (w), 1209 (w), 1154
(w), 1065 (m), 996 (s), 970 (m), 952 (m), 929 (w), 853 (m), 824 (w),
785 (s), 754 (m), 724 (m), 702 (s) cm–1. UV/Vis: λ (ε) = 594 (7900),
551 (16100), 424 (274600) nm. C38H22Br2N4SZn (791.89): calcd. C
57.64, H 2.80, N 7.08, S 4.05; found C 58.06, H 3.17, N 7.05, S
4.13.
C
92H104CoN4O6S6 (1613.16): calcd. C 68.50, H 6.50, N 3.47, S
11.39; found C 68.16, H 6.24, N 3.40, S 11.62.
{10-[2-(2,5-Dibromothien-3-yl)vinyl]-5,15-diphenylporphyrinato}-
copper(II) (16): (Method II) Compound 14 (300 mg, 543 µmol), 15
(240 mg, 633 µmol), DME (9 mL), NaH (60 % in mineral oil,
82 mg, 2.05 mmol), 22 h at r.t., adding H2O (25 mL), extraction
with CH2Cl2 (3ϫ30 mL), and purification by flash chromatog-
raphy (hexane/CH2Cl2, 1:1, Rf = 0.72) gave 16 (320 mg, 405 µmol,
74%); purple solid; m.p. 287 °C. MS (EI): m/z = 787/788/789/790/
791/792/793 (35/15/100/38/81/31/24) [M+·], 707/708/709/710/711/
712/713 (12/36/51/64/66/38/24) [M+· – Br], 627/628/629/620/621/
622/ 623 (8/20/15/32/16/33) [M+· – 2ϫBr]. MS (APCI, CHCl3): m/z
(%) = 788/789/790/791/792/793/794 (48/34/100/50/94/42/28) [M +
H+]. HRMS (APCI, CHCl3): calcd. for C38H23Br2CuN4S [M + H+]
(10-{2-[3,4ЈЈ-Bis(hexoxy)-2,2Ј:5Ј,2ЈЈ-terthiophen-3Ј-yl]vinyl}-5,15-di-
phenylporphyrinato)zinc(II) (22): (Method III) Compound 21
(160 mg, 202 µmol), 17 (140 mg, 613 µmol), Pd(PPh3)4 (40 mg,
35 µmol, 9 mol-%), DME (15 mL), 1  aqueous Na2CO3 (8 mL),
5 h reflux, adding H2O (30 mL), extraction with CH2Cl2
(3ϫ30 mL), and purification by flash chromatography (hexane/
CH2Cl2, 1:1; Rf = 0.90) gave 22 (130 mg, 130 µmol, 64%); dark
1
solid; m.p. 178 °C. H NMR (600 MHz): δ = 9.89 (s, 1 H, 15-H),
3
3
9.38 (d, J8,7 = 4.6 Hz, 2 H, 8-H), 9.31 (d, J16,17 = 15.8 Hz, 2 H,
3
3
787.9277; found 787.9306. FTIR: ν = 3098 (w), 3053 (w), 3027 (w),
˜
16-H), 9.16 (d, J13,12 = 4.4 Hz, 2 H, 13-H), 8.93 (d, J12,13
=
3
2922 (w), 2852 (w), 1598 (w), 1527 (w), 1489 (w), 1441 (w), 1381
(w), 1327 (w), 1208 (w), 1156 (w), 1065 (w), 995 (m), 965 (m), 951
(m), 928 (w), 906 (w), 857 (m), 823 (m), 783 (s), 745 (m), 725 (m)
cm–1. UV/Vis: λ (ε) = 582 (6200), 541 (16100), 419 (247500) nm.
C38H22Br2CuN4S (790.03): calcd. C 57.77, H 2.81, N 7.09, S 4.06;
found C 58.59, H 2.90, N 7.34, S 4.02.
4.4 Hz, 2 H, 12-H), 8.88 (d, J7,8 = 4.6 Hz, 2 H, 7-H), 8.18–8.14
(m, 4 H, 3-H), 7.86 (s, 1 H, 24-H), 7.81–7.73 (m, 6 H, 1,2-H), 7.43
(d, 3J17,16 = 15.8 Hz, 2 H, 17-H), 6.91 (d, J27,29 = 1.7 Hz, 1 H, 27-
4
4
4
H), 6.82 (d, J20,18 = 1.7 Hz, 1 H, 20-H), 6.09 (d, J29,27 = 1.7 Hz,
1 H, 29-H), 6.06 (d, J18,20 = 1.7 Hz, 1 H, 18-H), 3.91 (d, J36,37
4
3
=
3
6.5 Hz, 2 H, 36-H), 3.72 (d, J30,31 = 6.5 Hz, 2 H, 30-H), 1.81–1.75
(m, 2 H, 37-H), 1.58–1.51 (m, 2 H, 31-H), 1.51–1.44 (m, 2 H, 38-
H), 1.40–1.34 (m, 4 H, 39,40-H), 1.27–1.20 (m, 2 H, 32-H), 1.19–
1.11 (m, 4 H, 33,34-H), 0.96–0.91 (m, 3 H, 41-H), 0.77–0.72 (m, 3
H, 35-H) ppm. 13C NMR (150 MHz): δ = 157.6 (s, C-28), 157.5 (s,
{10-{2-[3,4ЈЈ-Bis(hexoxy)-2,2Ј:5Ј,2ЈЈ-terthiophen-3Ј-yl]vinyl}-5,15-
diphenylporphyrinato}copper(II) (18): (Method III) Compound 16
(383 mg, 485 µmol), 17 (332 mg, 1.45 mmol), Pd(PPh3)4 (70 mg,
61 µmol, 6 mol-%), DME (30 mL), 1  aqueous Na2CO3 (15 mL),
3 h reflux, adding H2O (50 mL), extraction with CH2Cl2 C-19), 149.8 (s, C-11), 149.58 (s, C-14), 149.56 (s, C-6), 148.6 (s, C-
(3 ϫ 70 mL), purification by flash chromatography (hexane/ 9), 142.6 (s, C-4), 137.1 (s, C-23), 136.3 (s, C-25), 134.9 (s, C-26),
CH2Cl2, 2:1, Rf = 0.54), and recrystallisation from MeOH/CH2Cl2 134.8 (d, C-17), 134.6 (d, C-3), 133.5 (s, C-21), 132.9 (s, C-22),
(40 mL/10 mL) gave 18 (400 mg, 401 µmol, 82%); purple solid; 132.4 (d, C-12), 131.9 (d, C-7), 131.7 (d, C-16), 131.5 (d, C-13),
m.p. 152 °C. MS (EI): m/z (%) = 995/996/997/998/999 (100/64/74/
129.9 (d, C-8), 127.4 (d, C-1), 126.6 (d, C-2), 122.2 (d, C-24), 120.6
39/19) [M]+·. MS (APCI, CHCl3): m/z (%) = 996/997/998/999/1000 (s, C-5), 119.1 (d, C-20), 117.5 (s, C-10), 116.5 (d, C-27), 105.5 (d,
(100/74/98/46/26) [M + H+]. HRMS (APCI, CHCl3): calcd. for C-15), 98.4 (d, C-18), 96.6 (d, C-29), 70.1 (t, C-36), 69.9 (t, C-30),
C H CuN O S [M + H+] 996.2590; found 996.2621. FTIR: ν =
31.6 (t, C-39), 31.4 (t, C-33), 29.2 (t, C-37), 30.0 (t, C-31), 25.7 (t,
C-38), 25.5 (t, C-32), 22.6 (t, C-34), 22.4 (t, C-40), 14.1 (q, C-41),
˜
58 53
4
2 3
3114 (w), 3050 (w), 2925 (w), 2855 (w), 1596 (w), 1553 (w), 1526
(m), 1489 (w), 1440 (w), 1350 (m), 1208 (w), 1165 (m), 1064 (m), 13.9 (q, C-35) ppm. MS (ESI MeOH): m/z (%) = 996/997/998/999/
995 (m), 967 (w), 954 (w), 921 (w), 841 (w), 814 (m), 786 (s), 750
1000/1001/1002 (100/68/92/60/70/38/20) [M+·/M + H+]. MS (APCI,
(m), 719 (m) cm–1. UV/Vis: λ (ε) = 586 (8200), 542 (15900), 417 MeOH/CHCl3): m/z (%) = 996/997/998/999/1000/1001/1002 (94/90/
(174400) nm. C58H52CuN4O2S3 (996.80): calcd. C 69.89, H 5.26, N 100/73/70/ 56/24) [M+·/M + H+]. HRMS (APCI, MeOH/CHCl3):
5.62, S 9.65; found C 68.07, H 5.12, N 5.49, S 9.30.
calcd. for C58H52N4O2S3Zn [M+·] 996.2538; found 996.2534. FTIR:
Eur. J. Org. Chem. 2010, 4426–4435
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4433

H.-H. Johannes et al.
ν = 3112 (w), 3050 (w), 2925 (w), 2854 (w), 1553 (m), 1524 (w), [M]+·. HRMS (EI): calcd. for C58H54N4O2S3 [M]+· 934.3409; found
FULL PAPER
˜
1486 (w), 1454 (w), 1439 (w), 1352 (m), 1210 (w), 1165 (m), 1062 934.3416. FTIR: ν = 3307 (w), 3112 (w), 3054 (w), 2924 (w), 2855
˜
(m), 995 (s), 967 (w), 953 (m), 921 (w), 843 (w), 814 (m), 782 (s),
(w), 1596 (w), 1552 (w), 1524 (m), 1455 (w), 1442 (w), 1403 (w),
750 (m) 720 (m) cm–1. UV/Vis: λ (ε) = 598 (10900), 552 (16600), 423 1352 (m), 1238 (w), 1165 (m), 1065 (w), 1025 (w), 1001 (w), 971
(201600) nm. C58H52N4O2S3Zn (998.66): calcd. C 69.76, H 5.25, N
5.61, S 9.63; found C 69.88, H 5.22, N 5.85, S 9.33.
(m), 956 (m), 928 (w), 847 (w), 788 (s), 722 (s) cm–1. UV/Vis: λ (ε)
= 654 (4700), 595 (sh.), 564 (12400), 518 (12300), 420 (183000) nm.
C58H54N4O2S3 (935.27): calcd. C 74.48, H 5.82, N 5.99, S 10.29;
found C 74.12, H 5.89, N 5.99, S 10.06.
10-[2-(2,5-Dibromothien-3-yl)vinyl]-5,15-diphenylporphyrin (23):
(Method II) Compound 19 (400 mg, 815 µmol), 15 (600 mg,
1.53 mmol), DME (10 mL), NaH (60 % in mineral oil, 215 mg,
5.36 mmol), 6.5 h reflux, adding H2O (30 mL), extraction with
CH2Cl2 (5ϫ50 mL), washing with brine (50 mL), and purification
by flash chromatography (hexane/CH2Cl2, 1:2; Rf = 0.81) gave 23
(360 mg, 494 µmol, 60%); purple solid; m.p. Ͼ350 °C. 1H NMR
{10-{2-[3,4ЈЈ-Bis(hexoxy)-2,2Ј:5Ј,2ЈЈ-terthiophen-3Ј-yl]vinyl}-5,15-
diphenylporphyrinato}cobalt(II) (25): (Method IB) Compound 24
(230 mg, 246 µmol), Co(OAc)2·4H2O (720 mg, 2.89 mmol), DMF
(15 mL), 2 h reflux, adding H2O (60 mL), extraction with CH2Cl2
(5ϫ100 mL), washing with brine (60 mL) and H2O (5ϫ100 mL)
gave 25 (150 mg, 151 µmol, 61 %); purple solid; m.p. 229 °C.
MS (ESI MeOH/CHCl3): m/z (%) = 991/992/993/994 (100/66/36/15)
[M+·/M + H+]. MS (APCI, CHCl3): m/z (%) = 992/993/994/995 (34/
100/68/38) [M + H+]. HRMS (APCI, CHCl3): calcd. for
3
(600 MHz): δ = 10.14 (s, 1 H, 15-H), 9.52 (d, J16,17 = 16.0 Hz, 1
3
3
H, 16-H), 9.49 (d, J8,7 = 4.7 Hz, 2 H, 8-H), 9.28 (d, J13,12
=
3
4.5 Hz, 2 H, 12,13-H), 8.96 (d, J12,13 = 4.4 Hz, 2 H, 12-H), 8.95
(d, J7,8 = 4.7 Hz, 2 H, 7-H), 8.25–8.21 (m, 4 H, 3-H), 7.83–7.77
3
(m, 6 H, 20-H), 7.80 (s, 1 H, 1,2-H), 7.27 (d, 3J17,16 = 16.0 Hz, 1 H,
17-H), –2.85 (s, 2 H, tautomeric NH) ppm. 13C NMR (150 MHz):
δ = 146.5 (br. signal, α-pyrrol-C-6,9,11,14), 141.7 (s, C-4), 139.9 (s,
C-19), 134.6 (d, C-3), 134.1 (d, C-17), 132.0 (d, C-16), 131.2 (br.
signal, β-pyrrol-C-7,12,13), 129.3 (br. signal, β-pyrrol-C-8), 127.8
(d, C-1), 127.7 (d, C-20), 126.8 (d, C-2), 120.0 (s, C-5), 116.1 (s, C-
10), 112.4 (s, C-21), 111.6 (s, C-18), 105.1 (d, C-15) ppm. MS (EI):
C H N CoO S [M + H+] 992.2663; found 992.2642. FTIR: ν =
˜
58 53
4
2 3
3113 (w), 3054 (w), 3023 (w), 2927 (m), 2853 (w), 1598 (w), 1527
(w), 1549 (m), 1529 (m), 1487 (w), 1467 (w), 1443 (w), 1386 (w),
1355 (m), 1209 (w), 1163 (m), 1068 (m), 1024 (w), 1000 (m), 951
(m), 854 (m), 816 (w), 792 (m), 778 (m), 749 (m), 722 (m) cm–1.
UV/Vis: λ (ε) = 578 (sh.), 533 (13500), 422 (136300) nm.
C58H52CoN4O2S3 (992.19): calcd. C 70.21, H 5.28, N 5.65, S 9.70;
found C 70.14, H 5.37, N 5.77, S 9.33.
m/z (%) = 726/727/728/729/730/731 (46/26/100/39/59/18) [M]+·
.
HRMS (EI): calcd. for C38H24Br2N4S [M]+· 726.0088; found
Supporting Information (see also the footnote on the first page of
this article): Contains extra cyclic voltammograms (CV) of 4, 8 and
12 as well as multisweep CVs of all compounds and CVs of NiDPP,
ZnDPP, CuDPP and CoDPP. Furthermore 1H/13C-NMR spectra
and the nomenclature of all carbons and hydrogens for signal
assignment are included.
726.0063. FTIR: ν = 3304 (w), 3092 (w), 3053 (w), 3026 (w), 1596
˜
(w), 1554 (w), 1477 (w), 1440 (w), 1403 (w), 1340 (w), 1240 (w),
1195 (w), 1152 (w), 1067 (w), 1048 (w), 1003 (w), 969 (m), 957 (m),
929 (m), 853 (m), 823 (w), 785 (s), 730 (s) cm–1. UV/Vis: λ (ε) =
652 (4300), 591 (sh.), 557 (11500), 517 (13900) 422 (272500) nm.
C38H24Br2N4S (728.50): calcd. C 62.65, H 3.32, N 7.69, S 4.40;
found C 62.15, H 3.43, N 7.97, S 4.43.
Acknowledgments
10-{2-[3,4ЈЈ-Bis(hexoxy)-2,2Ј:5Ј,2ЈЈ-terthiophen-3Ј-yl]vinyl}-5,15-
diphenylporphyrin (24): (Method III) Compound 23 (100 mg,
137 µmol), 17 (79 mg, 346 µmol), Pd(PPh3)4 (10 mg, 9 µmol, 3 mol-
%), DME (10 mL), 1  aqueous Na2CO3 (3 mL), 10 h reflux, add-
ing H2O (20 mL), extraction with CH2Cl2 (3ϫ40 mL), and purifi-
cation by flash chromatography (hexane/CH2Cl2 1:1; Rf = 0.47)
gave 24 (106 mg, 113 µmol, 82%); purple solid; m.p. 205 °C (DSC
peak onset). 1H NMR (600 MHz): δ = 10.04 (s, 1 H, 15-H), 9.59
We thank the Bundesministerium für Bildung und Forschung
(BMBF) and Deutsches Zentrum für Luft und Raumfahrt (DLR)
(FKZ 01BI565) for financial support.
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(d, J16,17 = 15.7 Hz, 1 H, 16-H), 9.51 (d, J8,7 = 4.6 Hz, 2 H, 8-
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25.5 (t, C-32), 22.6 (t, C-34), 22.4 (t, C-40), 14.1 (q, C-41), 13.9 (q,
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Received: October 30, 2009 (revised May 4, 2010)
Published Online: July 7, 2010
Eur. J. Org. Chem. 2010, 4426–4435
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4435