Selective cycloaddition of tetracyanoethene (TCNE) and 7,7,8,8-tetracyano- p-quinodimethane (TCNQ) to afford meso-substituted phenylethynyl porphyrins

Article abstract of DOI:10.1002/asia.201200179

π-Extended TCBD-porphyrins that contained a 1,1,4,4-tetracyanobuta-1,3- diene unit were prepared by a highly efficient [2+2] cycloaddition of tetracyanoethene (TCNE) or 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) with meso-substituted trans-A₂B₂-porphyrins that contained two phenylethynyl groups, followed by a retro-electrocyclization reaction. Depending on the electronic properties of the arylethynyl groups, the cycloaddition reaction took place exclusively on either one or two ethynyl moieties with high yield. The addition of TCNQ proceeded with complete regioselectivity. The resulting π-expanded TCBD-porphyrins had a hypsochromically shifted Soret band and showed unique, broad absorption in the visible region.

Full text of DOI:10.1002/asia.201200179

DOI: 10.1002/asia.201200179
Selective Cycloaddition of Tetracyanoethene (TCNE) and 7,7,8,8-Tetracyano-
p-quinodimethane (TCNQ) to Afford meso-Substituted Phenylethynyl
Porphyrins
Dominik Koszelewski, Agnieszka Nowak-Krꢀl, and Daniel T. Gryko*[a]
Abstract: p-Extended TCBD-porphyr-
ins that contained a 1,1,4,4-tetracyano-
buta-1,3-diene unit were prepared by
a highly efficient [2+2] cycloaddition
of tetracyanoethene (TCNE) or 7,7,8,8-
tetracyano-p-quinodimethane (TCNQ)
with meso-substituted trans-A2B2-por-
phyrins that contained two phenyle-
thynyl groups, followed by a retro-elec-
trocyclization reaction. Depending on
the electronic properties of the aryle-
thynyl groups, the cycloaddition reac-
tion took place exclusively on either
one or two ethynyl moieties with high
yield. The addition of TCNQ proceed-
ed with complete regioselectivity. The
resulting p-expanded TCBD-porphyr-
ins had
a hypsochromically shifted
Soret band and showed unique, broad
absorption in the visible region.
Keywords: chromophores · cyclo-
addition · porphyrins · tetracyanoe-
thene · UV/Vis spectroscopy
Introduction
structures have also emerged as promising candidates for
a wide range of applications, including artificial photosyn-
thetic systems,[8] optical limiters,[9] reverse saturable absorb-
ers (RSA),[10] biological imaging,[11] and dye-sensitized solar
cells (DSSCs).[12]
Arylethynylporphyrins have a significantly altered elec-
tronic structure compared to their parent macrocycle. The
incorporation of two arylethynyl moieties elongates their p-
conjugation pathway and improves the electronic interac-
tions between the phenyl substituents.[13] As part of our sys-
tematic investigation on the synthesis and reactivity of p-ex-
tended porphyrins,[14,15] herein, we report the first studies of
the reaction between meso-arylethynylporphyrins and
TCNE.
Donor–acceptor (D-A)-substituted conjugated organic chro-
mophores have received increasing interest because of their
desirable properties, such as high electrical conductivity and
large nonlinear optical (NLO) responses.[1] TCNE is one of
the strongest organic electron acceptors, and has found
widespread application in organic light-emitting diodes
(OLEDs), organic field-effect transistors (OFETs), and or-
ganic solar cells.[2,3] In 1981, Bruce et al. reported that the
reaction of electron-rich alkynes with TCNE afforded [2+2]
cycloaddition products, namely, cyclobutane derivatives,
which underwent ring-opening reactions to give their corre-
sponding 1,1,4,4-tetracyano-1,3-butadienes (TCBDs).[4] Sub-
sequently, Diederich and co-workers reported that a variety
of N,N-dialkylaniline-substituted alkynes reacted with
TCNE to give their corresponding TCBDs in high yields.
The same group also discovered that this new class of chro-
mophores was characterized by intense intramolecular
charge-transfer (CT) interactions with absorption maxima in
the visible region, as well as promising third-order optical
nonlinearities.[5] Recently, other groups have reported the
addition of TCNE to heterocyclic alkynes.[6]
Results and Discussion
We have designed a small library of trans-A2B2-porphyrins
that contained carbon–carbon triple bonds with substituted
phenyl units at their two meso-positions. These substituents
were carefully chosen to afford porphyrins with various elec-
tronic properties.
Over the last two decades, meso-arylethynylporphyrins
have received considerable attention in the field of materials
chemistry owing to their unique optical properties.[7] These
We envisioned that these prospective addition products
would possess rather poor solubility unless suitable substitu-
ents were placed at the remaining two meso-positions.
Indeed, in most cases we used tris(alkyloxyphenyl)substitu-
ents, which afforded products with high solubility in non-
polar organic solvents.
[a] Dr. D. Koszelewski, A. Nowak-Krꢀl, Prof. D. T. Gryko
Institute of Organic Chemistry
Readily available 3,4,5-trihydroxybenzaldehyde[16] was al-
kylated under classical Williamson conditions with alkyl bro-
mides or iodides to give 3,4,5-trialkoxybenzaldehydes 1 and
2.[7] These aldehydes were reacted with dipyrrane[18] and tri-
fluoroacetic acid to give A2-porphyrins in 48–52% yield, fol-
Polish Academy of Sciences
01-224 Warszaw, Kasprzaka 44/52 (Poland)
Fax : (+48)226326681
E-mail: dtgryko@icho.edu.pl
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201200179.
Chem. Asian J. 2012, 7, 1887 – 1894
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1887

FULL PAPER
lowed by bromination with N-bromosuccinimide (NBS),
thereby leading to porphyrins 3 and 4 in 98% and 95%
yield, respectively (Scheme 1). Finally, the target meso-ary-
lethynyl trans-A2B2-porphyrins, which contained 3,4,5-
(OC10H21)3C6H2 (11, 12, 14–16) and 3,4,5-(OC11H23)3C6H2
groups (10, 13), were synthesized in 63–85% yield through
Sonogashira coupling, which allowed the direct cross-cou-
pling of terminal alkynes 5–9 with porphyrin halides under
mild conditions in the presence of catalytic [Pd2ACTHNUTRGNEN(UG dba)3],
AsPh3 as the co-catalyst, and an aliphatic amine.[19] The re-
maining porphyrins, which contained 3,4,5-tri(tert-butoxycar-
bonylmethyloxy)phenyl- (18, 19) and mesityl (17) substitu-
ents, were obtained according to our recently reported pro-
cedure, starting from phenylpropargyl aldehydes and dipyr-
ranes, by using
a
[2+2] condensation approach
(Scheme 2).[14] Subsequently, these porphyrins (10–19) were
treated with TCNE or TCNQ in CH2Cl2 at room tempera-
ture (Scheme 2, Scheme 3, Table 1).
Table 1. Reactions of meso-arylethynyl-substituted porphyrins with
TCNE and TCNQ.[a]
Entry
Substrate
R2
Product
t [h]
1.5
24
2
48
8
3
Yield [%][b]
95[c]
36
81
86
1
2
3
4
5
6
7
8
10
11
12
12
17
13
14
15
15
16
18
19
19
p-(CH3)2NC6H4
p-(CH3)2NC6H4
p-MeOC6H4
p-MeOC6H4
p-MeOC6H4
6-MeOC10H6
n-C4H9
20
26
21
27
22
23
–
24
28
25
–
80
86
4
4
n.d.[d]
83
Ph
Ph
9
48
15
26
24[f]
48[g]
80
10
11
12
13
p-CF3C6H4
p-CNC6H4
p-NO2C6H4
p-NO2C6H4
98
0[e]
0[e]
0[e]
–
–
[a] All reactions were performed on a 0.02 mmol scale in CH2Cl2 at ambi-
ent temperature with 2 equiv of TCNE or TCNQ; [b] yields of isolated
product; [c] calculated for the mixture of isomers; [d] product decom-
posed during purification; [e] substrate was recovered; [f] reaction with
TCNE; [g] reaction with TCNQ.
Scheme 1. Synthesis of meso-phenylethynyl-substituted trans-A2B2-por-
phyrins. TFA=trifluoroacetic acid.
The addition of TCNE or TCNQ to a triple bond afforded
the corresponding products (20–28) in very high yields (in
most cases), even in the presence of some strongly electron-
withdrawing groups at the para position of the phenylethyn-
yl moiety (Table 1). This result was in contrast with earlier
reports, which showed that the addition of TCNE could only
take place if at least one aromatic unit contained a strongly
electron-donating substituent (NMe2, OMe, or thio-
phene).[5,6] Apparently, in our case, the porphyrin acted as
an electron-donating “substituent”, which, given its propen-
sity for electrophilic aromatic substitution, was not totally
unexpected. Moreover, mono-cycloaddition occurred in
most cases, thus suggesting that strong conjugation between
the newly formed electron-withdrawing group at the meso
position of the porphyrin deactivated the remaining triple
bond.
Abstract in Polish: W wyniku reakcji cykloaddycji tetracyja-
noetylenu (TCNE) oraz pochodnej TCNQ do wia˛zania po-
trꢀjnego trans podstawionych porfiryn i naste˛pczej reakcji
retro-elektrocyklizacji otrzymano serie˛ nowych TCBD-porfi-
ryn zawieraja˛cych jednostke˛ 1,1,4,4-tetracyjano-1,3-dienu. W
´
zalez˙nosci od charakteru elektronowego podstawnika grupy
´
etynylofenylowej otrzymano z wysoka˛ selektywnoscia˛ jak
´
´
i wydajnoscia˛ produkty mono ba˛dz di-podstawione. Tak
otrzymane zwia˛zki charakteryzuja˛ sie˛ hipsochromowym
przesunie˛ciem pasma Soreta oraz szerszym pasmem absorp-
cji w zakresie widzialnym.
In view of the excellent yield of TCBD-porphyrin 25, it
was rather unexpected that trans-A2B2-porphyrins 18 and
1888
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Chem. Asian J. 2012, 7, 1887 – 1894

Synthesis of meso-Substituted Phenylethynyl Porphyrins
19, which contained strongly
electron-withdrawing cyano-
and nitro substituents, respec-
tively, as well as 3,4,5-tris(tert-
butoxycarbonylmethyloxy)-
phenyl groups, were unreactive
(Table 1, entries 11–13). We
presumed that the difference in
the electronic influence be-
tween the 3,4,5-trialkoxyphenyl
substituent and its analogue
that
contained
three
OCH2CO2tBu groups was min-
iscule and could not explain the
difference in reactivity between
porphyrins 16 and 18–19. Con-
sequently, the only probable ex-
planation lay in a difference be-
tween the nature of these two
electron-withdrawing
groups
(CF3: inductive effect, CN: res-
onance effect). Heating from
ambient temperature up to
1008C did not improve the
yield of this reaction. The elec-
tronic nature of the substituent
strongly affected the reaction
time, which was in the range
Scheme 2. Reaction between TCNE and meso-phenylethynyl-substituted trans-A2B2-porphyrins 10–19.
from 1.5 hours for amino-substituted porphyrin 10 to
15 hours for trifluoromethyl-porphyrin 16 (Table 1, entries 1
and 10). Performing these reactions with either a larger
excess of TCNE or in boiling toluene led to the partial de-
composition of the starting material. With TCNQ, a longer
reaction time of up to 48 hours was required. All newly pre-
pared TCBD-porphyrins (21–28) were brownish semi-solids
that were stable at ambient temperature under air and well-
soluble in common organic solvents, such as CH2Cl2, THF,
toluene, and n-hexane. The use of porphyrin 14, which con-
tained two n-hexynyl substituents, unexpectedly led to com-
plete decomposition during the attempted work-up to afford
a dark, insoluble, polymeric material (Table 1, entry 7).
Me2N-substituted porphyrin 10 reacted with TCNE to
form a bis-adduct, TCBD-porphyrin 20. Although the reac-
tion time was very short (1.5 hours), the bis-adduct was
formed in 95% yield (Table 1, entry 1). Directly after the re-
action had been completed, the product was observed as
a single spot by TLC; however, after a couple of hours, TLC
analysis showed two spots that were the same color and
1
only slightly different in their retention factor (Rf). H NMR
spectroscopy, as well as MS, indicated that spontaneous iso-
merization had occurred. Performing an analogous reaction
with TCNQ afforded mono-adduct 26 in moderate yield
(36%) after 24 hours (Table 1, entry 2). Owing to the fact
that the dimethylanilino moiety was the superior electron
donor and -activator (Hammett constant sP
only one regioisomer was isolated and verified by
2D NOESY NMR spectroscopy (see the Supporting Infor-
G
Scheme 3. Reaction between TCNQ and meso-phenylethynyl-substituted
trans-A2B2-porphyrins 11, 12, 16, and 19.
Chem. Asian J. 2012, 7, 1887 – 1894
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
1889

Daniel T. Gryko et al.
FULL PAPER
mation). No side-products were formed in the solution-
phase reactions, as determined by 1H NMR spectroscopy.
Significant influence on the reaction time was observed
for trans-A2B2-porphyrins that contained two mesityl sub-
stituents at the meso positions. The corresponding TCBD-
porphyrin (22) was obtained in 80% yield after 8 hours,
versus 2 and 3 hours for TCBD-porphyrins 21 and 23, re-
spectively (Table 1, entries 3, 5, and 6). Substantially longer
reaction times, up to 48 hours, were also required in the re-
action between TCNQ and porphyrins 12 and 15, thereby
leading to their corresponding mono-adducts (27 and 28, re-
spectively) with high yields (86 and 80%, respectively;
Table 1, entries 4 and 9). These results clearly demonstrated
the influence of substituents on the course of the reaction
with porphyrins that exhibited strong electronic interactions
between the phenyl substituents.
Figure 2. Electronic absorption spectra of trans-A2B2-porphyrin 10 (solid
line) and TCBD-porphyrin 20 (dashed line) in CCl4 at 298 K.
A comparison of the UV/Vis spectra of TCBD-porphyrin
24 and porphyrin 15 showed a distinct hypsochromic shift of
the Soret band (about 15 nm). Slight broadening of the
Soret band was accompanied by a decrease in the molar ex-
tinction coefficient (e=334000 dm3 molÀ1 cmÀ1 for porphyrin
15 versus e=221000 dm3 molÀ1 cmÀ1 for TCBD-porphyrin
24; Figure 1). The analogous phenomenon was observed in
that was present in the UV/Vis spectra from 500 nm to the
NIR region probably involved charge transfer from the ani-
line to the cross-conjugated tetracyanobutadiene moiety.
Comparison of the spectrum of TCBD-porphyrin 20 with
that of an analogous dye that was prepared by Diederich
and co-workers from TCNE and 1,4-bis(4-aminophenylethy-
nyl)benzene showed the same features, that is, strong peak-
broadening between 500–800 nm. A hypsochromic shift of
the Soret band for TCBD-porphyrins 20–25 reflected the
lower level of conjugation of the porphyrin core with
TCBDs compared to porphyrins 10–13 and 15–17, which
contained two arylethynyl units. Presumably, the presence of
two hydrogen atoms at the b position of the porphyrin core
forced the TCBD unit to be almost perpendicular to the
porphyrin plane. On the other hand, the electronic commu-
nication was strong enough to alter the electron density of
the porphyrin unit and prevent a second cycloaddition.
It is known that porphyrins that are substituted at the
meso positions with only one phenylethynyl unit still show
characteristic sharp Q bands. The lack of these bands in the
electronic spectra of compounds 20–28 suggested that their
electronic structure was strongly affected by the adjacent
TCBD unit. Owing to significant peak-broadening and to
the complexity of the system, we were unable to determine
whether phenylethynylporphyrin-to-TCBD, substituted aryl-
to-TCBD, or a combination of both CT transitions were
active. Porphyrins 20–28 did not display any fluorescence, in
analogy to the TCNE adducts of BODIPY.[6a] This result
was most-probably caused by electron transfer from the
electron-rich p-extended porphyrin to the 1,1,4,4-tetracya-
no-1,3-butadiene moiety, followed by deactivation by vibra-
tional relaxation.
Figure 1. Electronic absorption spectra of trans-A2B2-porphyrin 15 (solid
line) and TCBD-porphyrin 24 (dashed line) in CCl4 at 298 K.
all other cases. The two Q bands near 600 and 690 nm in the
spectra of trans-A2B2-porphyrins (2.06 and 1.79 eV, respec-
tively) were replaced by
a very broad intramolecular
charge-transfer (CT) band with end-absorptions into the
near infrared (NIR) region (see the Supporting Information,
Figure S1). This result was in strong contrast to the structur-
ally smaller TCBDs reported by Diederich and co-workers,
which displayed only CT bands.
Compared to substrate 10, TCBD-porphyrin 20 exhibited
an even more pronounced hypsochromic shift (32 nm,
0.19 eV) of the Soret band, which was accompanied by
a strong decrease in the molar extinction coefficient (e=
157000 dm3 molÀ1 cmÀ1 at 433 nm; Figure 2). This shift was
not observed in the case of TCBD-porphyrin 26. The tail
Conclusions
A new family of chromophores was synthetized by the
mono- or double [2+2] cycloaddition of TCNE or TCNQ to
meso-substituted phenylethynylporphyrins, followed by
1890
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Chem. Asian J. 2012, 7, 1887 – 1894

Synthesis of meso-Substituted Phenylethynyl Porphyrins
retro-electrocyclization.[20] The scope and efficiency of this
atom-economic transformation was demonstrated by per-
forming the reaction with a series of acetylenic porphyrins.
The reaction of TCNE with these substrates added a new di-
mension to this chemistry owing to the exceptional steric
hindrance that was imparted by the porphyrin ring, which
forced a unique geometry (and hence UV/Vis absorption) of
the final products. Despite the non-planarity of these sys-
tems, strong intramolecular charge-transfer (CT) interac-
tions were apparent. Depending on the electronic character
of the substituents, the reaction exclusively afforded mono-
or di-substituted TCBD derivatives in very high yields. The
full scope of the reaction between tetracyanoethene or
7,7,8,8-tetracyanoquinodimethane and various meso-substi-
tuted ethynylporphyrins is currently under investigation
within the group. The applications of this readily available
new class of D–A compounds in NLO and other optoelec-
tronic devices represent a worthwhile objective for future
work.
(%) for C92H142N4O6: C 78.92, H 10.22 N 4.00; found: C 78.71 H 10.18,
N 3.96.
5,15-Bis-(3,4,5-triundecyloxyphenyl)-porphyrin
The product was obtained in 52% yield (0.59 g, 0.40 mmol). Rf =0.39
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À3.11 (brs, 2H; NH), 0.83–0.86 (m, 12H; CH3), 0.88–0.91 (m, 6H; CH3),
1.23–1.26 (m, 80H; CH3), 1.34–1.40 (m, 12H; CH2), 1.64–1.68 (m, 4H;
CH2), 1.89–1.91 (m, 8H; CH2), 1.96–1.99 (m, 4H; CH2), 4.13 (t, J=
6.5 Hz, 8H; OCH2), 4.32 (t, J=6.5 Hz, 4H; OCH2), 7.47 (s, 4H; ArH),
9.18 (d, J=5.0 Hz, 4H; b-H), 9.38 (d, J=5.0 Hz, 4H; b-H), 10.32 ppm (s,
2H; meso-H); UV/Vis (CCl4): lmax (e)=413 (319600), 505 (16100), 230
(14700), 540 (6200), 578 (5000), 636 nm (1200 molÀ1 dm3 cmÀ1); LRMS
(FD): m/z calcd for C98H154N4O6: 1484.30; found: 1484.2 (the isotope pro-
files matched); elemental analysis calcd (%) for C98H154N4O6 C 79.30,
H 10.46, N 3.77; found: C 79.50, H 10.73, N 3.50.
General Procedure for the Synthesis of 5,15-Dibromo-porphyrins
N-bromosuccinimide (NBS, 125 mg, 0.70 mmol) was added to a solution
of A2-porphyrin (0.35 mmol) in CHCl3 (40 mL) at ambient temperature
and the mixture was stirred for 1 h. The bromination reaction was
quenched by the addition of acetone (5 mL) and the solvent was re-
moved under reduced pressure. The crude material was purified by
column chromatography on silica gel (hexanes/EtOAc) and by size-exclu-
sion chromatography (toluene).
Experimental Section
General
5,15-Dibromo-10,20-bis-(3,4,5-tridecyloxyphenyl)-porphyrin (3)
The product was obtained in 98% yield (0.53 g, 0.34 mmol). Rf =0.42
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À2.72 (brs, 2H; NH), 0.83 (m, 12H; CH3), 0.92 (m, 6H; CH3), 1.22–1.54
(m, 80H; CH2), 1.69 (m, 4H; CH2), 1.90 (m, 8H; CH2), 2.00 (m, 4H;
CH2), 4.10 (t, J=6.4 Hz, 8H; OCH2), 4.31 (t, J=6.4 Hz, 4H; OCH2),
7.37 (s, 4H; ArH), 8.94 (d, J=5.0 Hz, 4H; b-H), 9.59 ppm (d, J=5.0 Hz,
4H; b-H); UV/Vis (CCl4): lmax (e)=428 (296100), 523 (15800), 306
All chemicals were used as received unless otherwise stated. Reagent-
grade solvents (CH2Cl2, hexanes) were distilled prior to use. All H NMR
1
spectra were collected on a 500 or 600 MHz spectrometer. Chemical
shifts (d) are reported in ppm with TMS as an internal reference; J
values are given in Hz. UV/Vis absorption spectra were recorded in
CCl4; purge gas was high-purity argon. Column chromatography was per-
formed on silica gel (200–400 mesh) or alumina. Preparative scale size-
exclusion chromatography (SEC) was carried out by using BioRad Bio-
Beads SX-1 with toluene as an eluent. Mass spectra were obtained by
using field-desorption mass spectrometry (FD-MS). 3,4,5-Trinonyloxy-
benzaldehyde (1), 3,4,5-tridecyloxybenzaldehyde (2), as well as trans-
A2B2-porphyrins 17--19, were prepared according to literature proce-
dures.[14, 17]
(13700),
558
(10500),
603
(4600),
662
(4400),
490 nm
(4300 molÀ1 dm3 cmÀ1); LRMS (FD): m/z calcd for C92H140Br2N4O6:
1557.93; found: 1557.9 (the isotope profiles matched); elemental analysis
calcd (%) for C92H140Br2N4O6: C 70.93, H 9.06, N 3.60; found: C 70.99,
H 9.31, N 3.43.
5,15-Dibromo-10,20-bis-(3,4,5-triundecyloxyphenyl)-porphyrin (4)
The product was obtained in 95% yield (0.55 g, 0.33 mmol). Rf =0.41
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À2.72 (brs, 2H; NH), 0.84–0.86 (m, 12H; CH3), 0.87–0.91 (m, 6H; CH3),
1.28–1.31 (m, 80H; CH2), 1.35–1.40 (m, 12H; CH2), 1.62–1.68 (m, 4H;
CH2), 1.85–1.91 (m, 8H; CH2), 1.98–2.03 (m, 4H; CH2), 4.10 (t, J=
6.5 Hz, 8H; OCH2), 4.32 (t, J=6.5 Hz, 4H; OCH2), 7.37 (s, 4H; ArH),
8.95 (d, J=5.0 Hz, 4H; b-H), 9.59 ppm (d, J=5.0 Hz, 4H; b-H); UV/Vis
(CCl4): lmax (e)=428 (307800), 523 (16600), 558 (11000), 603 (4900), 662
(4600), 489 nm (4500 molÀ1 dm3 cmÀ1); LRMS (FD): m/z calcd for
C98H152Br2N4O6: 1642.09; found: 1642.0 (the isotope profiles matched);
elemental analysis calcd (%) for C98H152Br2N4O6: C 71.68, H 9.33, N 3.41;
found: C 71.64, H 9.60, N 3.16.
General Procedure for the Synthesis of A2-Porphyrins
A mixture of dipyrrane (15.5 mmol) and an aldehyde (15.5 mmol) in
CH2Cl2 (2 L) was purged with argon. CF3COOH (0.75 mL, 9.8 mmol)
was added dropwise and the flask was kept in the dark with aluminum
foil. The solution was stirred under an argon atmosphere at RT for 3 h.
The reaction was quenched by the addition of 2,3-dichloro-5,6-dicyano-
1,4-benzoquinone (DDQ; 4.5 g, 20 mmol) and the solution was stirred for
an additional 30 min. The mixture was neutralized with triethylamine
(15 mL) and then directly poured on top of a silica gel column that was
packed with CH2Cl2. The column was eluted with CH2Cl2 and the frac-
tions that contained product were collected, concentrated under reduced
pressure, and purified by column chromatography on silica gel (hexanes/
EtOAc). The resulting viscous violet residue was purified by size-exclu-
sion chromatography (toluene).
General Procedure for the Synthesis of trans-A2B2-Porphyrins
The mixture of 5,15-dibromo-porphyrin (0.04 mmol) and corresponding
arylacetylene (0.1 mmol) in THF (5 mL) with toluene (0.5 mL) and trie-
thylamine (1 mL) was deoxygenated by freeze–pump–thaw cycles and
5,15-Bis-(3,4,5-tridecyloxyphenyl)-porphyrin
purged with argon gas in
a Schlenk flask. Triphenylarsine (6.5 mg,
The product was obtained in 48% yield (0.52 g, 0.37 mmol). Rf =0.40
(hexanes/EtOAc 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À3.11 (brs, 2H; NH), 0.83 (m, 12H; CH3), 0.92 (m, 6H; CH3), 1.22–1.54
(m, 80H; CH2), 1.69 (m, 4H; CH2), 1.90 (m, 8H; CH2), 2.00 (m, 4H;
CH2), 4.13 (t, J=6.4 Hz, 8H; OCH2), 4.33 (t, J=6.4 Hz, 4H; OCH2),
7.52 (s, 4H; ArH), 9.18 (d, J=5.0 Hz, 4H; b-H), 9.37 (d, J=5.0 Hz, 4H;
b-H), 10.32 ppm (s, 2H; meso-H); UV/Vis (CCl4): lmax (e)=412
(286000), 504 (17500), 299 (16600), 539 (8000), 578 (6700), 635 nm
(2900 molÀ1 dm3 cmÀ1); LRMS (FD): calcd for C92H142N4O6: 1400.14;
found: 1400.9 (the isotope profiles matched); elemental analysis calcd
0.02 mmol) and [Pd2A(dba)3] (25 mg, 30 mmol) were added and the mixture
CTHUNGTRENNUNG
was stirred at 308C in the dark for 24 h. The crude mixture was filtered
through celite. The organic layer was separated, dried with Na2SO4, and
the solvent was removed under reduced pressure. The crude green prod-
uct was purified by column chromatography on silica gel (hexanes/
EtOAc) and size-exclusion chromatography (toluene).
Chem. Asian J. 2012, 7, 1887 – 1894
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
1891

Daniel T. Gryko et al.
FULL PAPER
5,15-Bis-(3,4,5-trisundecyloxyphenyl)-10,20-bis-(4-ethynyl-N,N-
dimethylaniline)-porphyrin (10)
(m, 4H; CH2), 3.01 (t, J=7.4 Hz, 4H; CH2), 4.11 (t, J=6.4 Hz, 8H;
CH2), 4.31 (t, J=6.4 Hz, 4H; CH2), 7.39 (s, 4H; ArH), 8.89 (d, J=
5.0 Hz, 4H; b-H), 9.56 ppm (d, J=5.0 Hz, 4H; b-H); UV/Vis (CCl4): lmax
(e)=434 (399800), 580 (36600), 539 (16700), 680 (12200), 618 nm
(7200 molÀ1 dm3 cmÀ1); LRMS (FD): m/z calcd for C104H158N4O6: 1560.40;
found: 1560.2 (the isotope profiles matched).
The product was obtained in 85% yield (60 mg, 0.03 mmol). Rf =0.45
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À1.73 (br s, 2H; NH), 0.84–0.86 (m, 12H; CH3), 0.87–0.91 (m, 6H; CH3),
1.28–1.31 (m, 80H; CH2), 1.35–1.40 (m, 12H; CH2), 1.62–1.68 (m, 4H;
CH2), 1.85–1.91 (m, 8H; CH2), 1.98–2.03 (m, 4H; CH2), 3.11 (s, 12H;
NCH3), 4.12 (t, J=6.5 Hz, 8H; OCH2), 4.30 (t, J=6.5 Hz, 4H; OCH2),
6.88 (d, J=9.0 Hz, 4H; ArH), 7.40 (s, 4H; ArH), 7.88 (d, J=9.0 Hz, 4H;
ArH), 8.88 (d, J=5.0 Hz, 4H; b-H), 9.63 ppm (d, J=5.0 Hz, 4H; b-H);
UV/Vis (CCl4): lmax (e)=465 (279600), 628 (57500), 287 (46600), 328
(44900), 712 nm (3600 molÀ1 dm3 cmÀ1); LRMS (FD): m/z calcd for
C118H172N6O6: 1770.67; found: 1770.2 (the isotope profiles matched); ele-
mental analysis calcd (%) for C118H172N6O6: C 80.04, H 9.79, N 4.75;
found: C 80.29, H 9.75, N 4.45.
5,15-Bis-(3,4,5-trisdecyloxyphenyl)-10,20-bis-(phenylethynyl)-porphyrin
(15)
The product was obtained in 85% yield (55 mg, 0.03 mmol). Rf =0.45
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À1.97 (brs, 2H; NH), 0.83–0.89 (m, 12H; CH3), 0.92–0.98 (m, 6H; CH3),
1.22–1.54 (m, 80H; CH2), 1.69 (m, 4H; CH2), 1.90–1.92 (m, 8H; CH2),
2.00 (m, 4H; CH2), 4.13 (t, J=6.4 Hz, 8H; OCH3), 4.32 (t, J=6.4 Hz,
4H; OCH3), 7.41 (s, 4H; ArH), 7.48–7.54 (m, 2H; ArH), 7.56–7.60 (m,
4H; ArH), 8.00–8.06 (m, 4H; ArH), 8.95 (d, J=5.0 Hz, 4H; b-H),
9.68 ppm (d, J=5.0 Hz, 4H; b-H); UV/Vis (CCl4): lmax (e)=445
(334200), 600 (44300), 693 (20800), 287 (19500), 558 (8100), 518 nm
(4631 molÀ1 dm3 cmÀ1); LRMS (FD): m/z calcd for C108H150N4O6: 1600.37;
found: 1600.2 (the isotope profiles matched); elemental analysis calcd
(%) for C108H150N4O6: C 81.05, H 9.45, N 3.50; found: C 81.33, H 9.49,
N 3.38.
5,15-Bis-(3,4,5-trisdecyloxyphenyl)-10,20-bis-(4-ethynyl-N,N-
dimethylaniline)-porphyrin (11)
The product was obtained in 78% yield (53 mg, 0.03 mmol). Rf =0.40
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À1.90 (brs, 2H; NH), 0.82–0.90 (m, 12H; CH3), 0.92–0.98 (m, 6H; CH3),
1.22–1.54 (m, 80H; CH2), 1.69 (m, 4H; CH2), 1.90 (m, 8H; CH2), 2.00
(m, 4H; CH2), 3.11 (s, 12H; NCH3), 4.12 (t, J=6.4 Hz, 8H; OCH2), 4.31
(t, J=6.4 Hz, 4H; OCH2), 6.87 (d, J=8.5 Hz, 4H; ArH), 7.40 (s, 4H;
ArH), 7.88 (d, J=8.5 Hz, 4H; ArH), 8.87 (d, J=5.0 Hz, 4H; b-H),
9.63 ppm (d, J=5.0 Hz, 4H; b-H); UV/Vis (CCl4): lmax (e)=464
(285000), 628 (58000), 712 nm (36000 molÀ1 dm3 cmÀ1); LRMS (FD): m/z
calcd for C110H160N6O6: 1686.56; found: 1686.2 (the isotope profiles
matched); elemental analysis calcd (%) for C110H160N6O6: C 79.76,
H 9.56, N 4.98; found: C 79.37, H 10.23, N 4.49.
5,15-Bis-(3,4,5-trisdecyloxyphenyl)-10,20-bis-(4-
trifluoromethylphenylethynyl)-porphyrin (16)
The product was obtained in 72% yield (50 mg, 0.03 mmol). Rf =0.43
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À2.02 (brs, 2H; NH), 0.82–0.90 (m, 12H; CH3), 0.92–0.98 (m, 6H; CH3),
1.22–1.54 (m, 80H; CH2), 1.69 (m, 4H; CH2), 1.90 (m, 8H; CH2), 2.00
(m, 4H; CH2), 4.13 (t, J=6.4 Hz, 8H; OCH2), 4.31 (t, J=6.4 Hz, 4H;
OCH2), 7.41 (s, 4H; ArH), 7.83 (d, J=8.5 Hz, 4H; ArH), 8.12 (d, J=
8.5 Hz, 4H; ArH), 8.98 (d, J=5.0 Hz, 4H; b-H), 9.65 ppm (d, J=5.0 Hz,
4H; b-H); UV/Vis (CCl4): lmax (e)=454 (410400), 612 (57800), 701
(32600), 333 (27800), 525 nm (7600 molÀ1 dm3 cmÀ1); LRMS (FD): m/z
calcd for C110H148F6N4O6: 1736.37; found: 1736.0 (the isotope profiles
matched); elemental analysis calcd (%) for C110H148F6N4O6: C 76.09,
H 8.59, N 3.23; found: C 75.81, H 8.56, N 3.04.
5,15-Bis-(3,4,5-trisdecyloxyphenyl)-10,20-bis-(4-methoxyphenylethynyl)-
porphyrin (12)
The product was obtained in 78% yield (52 mg, 0.03 mmol). Rf =0.42
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À1.90 (brs, 2H; NH), 0.82–0.90 (m, 12H; CH3), 0.92–0.98 (m, 6H; CH3),
1.22–1.54 (m, 80H; CH2), 1.69 (m, 4H; CH2), 1.90 (m, 8H; CH2), 2.00
(m, 4H; CH2), 3.94 (s, 6H; OCH3), 4.13 (t, J=6.4 Hz, 8H; OCH2), 4.32
(t, J=6.4 Hz, 4H; OCH2), 7.10 (d, J=8.5 Hz, 4H; ArH), 7.41 (s, 4H;
ArH), 7.95 (d, J=8.5 Hz, 4H; ArH), 8.92 (d, J=5.0 Hz, 4H; b-H),
9.65 ppm (d, J=5.0 Hz, 4H; b-H); UV/Vis (CCl4): lmax (e)=449
(402600), 607 (52600), 698 (26000), 523 nm (6400 molÀ1 dm3 cmÀ1);
LRMS (FD): m/z calcd for C110H154N4O8: 1660.43; found: 1660.0 (the iso-
tope profiles matched); elemental analysis calcd (%) for C110H154N4O8
C 79.57, H 9.35, N 3.37; found: C 79.30, H 9.54, N 3.59.
General Procedure for the Synthesis of TCBD-Porphyrins
TCNE (8.0 mg, 0.06 mmol) or TCNQ (13.0 mg, 0.06 mmol) were added
to
a solution of trans-A2B2-porphyrin (1–10, 0.03 mmol) in CH2Cl2
(3 mL) and the mixture was stirred at ambient temperature. Evaporation
of solvent under reduced pressure followed by column chromatography
on silica gel (hexanes/EtOAc, 95:5) and size-exclusion chromatography
(toluene) afforded the product as a brownish solid.
5,15-Bis-(3,4,5-trisundecyloxyphenyl)-10,20-bis-{(4-ethynyl-N,N-
5,15-Bis-(3,4,5-trisundecyloxyphenyl)-10,20-bis-(2-ethynyl-6-
dimethylaniline)-1,3-diene-1,1,4,4-tetracarbonitrile)}-porphyrin (20)
methoxynaphthalene)-porphyrin (13)
The product was obtained in 95% yield (58 mg, 0.03 mmol). Rf =0.32
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À2.10 (brs, 2H; NH), À2.01 ppm (brs, 2H; NH); UV/Vis (CCl4): lmax
(e)=433 nm (157300 molÀ1 dm3 cmÀ1); LRMS (FD): m/z calcd for
C130H172N14O6: 2026.91; found: 2027.0 (the isotope profiles matched); ele-
mental analysis calcd (%) for C130H172N14O6: C 77.04, H 8.53, N 9.67;
found: C 77.16, H 8.44, N 9.30.
The product was obtained in 85% yield (63 mg, 0.03 mmol). Rf =0.42
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À1.87 (brs, 2H; NH), 0.84–0.86 (m, 12H; CH3), 0.87–0.91 (m, 6H; CH3),
1.28–1.31 (m, 80H; CH2), 1.35–1.40 (m, 12H; CH2), 1.62–1.68 (m, 4H;
CH2), 1.85–1.91 (m, 8H; CH2), 1.98–2.03 (m, 4H; CH2), 3.99 (s, 6H;
OCH3), 4.14 (t, J=6.5 Hz, 8H; OCH2), 4.33 (t, J=6.5 Hz, 4H; OCH2),
7.20–7.21 (m, 2H; ArH), 7.23–7.24 (m, 1H; ArH), 7.25–7.26 (m, 1H;
ArH), 7.44 (s, 4H; ArH), 7.86–7.87 (m, 4H; ArH), 7.99–8.00 (m, 2H;
ArH), 8.42–8.43 (m, 2H; ArH), 8.96 (d, J=5.0 Hz, 4H; b-H), 9.73 ppm
(d, J=5.0 Hz, 4H; b-H); UV/Vis (CCl4): lmax (e)=454 (410400), 612
(57800), 333 (27800), 525 nm (7600 molÀ1 dm3 cmÀ1); LRMS (FD): m/z
calcd for C124H170N4O8: 1844.71; found: 1844.0 (the isotope profiles
matched); elemental analysis calcd (%) for C124H170N4O8: C 80.74,
H 9.29, N 3.04; found: C 80.39, H 9.26, N 2.69.
5,15-Bis-(3,4,5-trisdecyloxyphenyl)-10-(4-methoxyphenylethynyl)-20-{(4-
methoxyphenylethynyl)-1,3-diene-1,1,4,4-tetracarbonitrile)}-porphyrin (21)
The product was obtained in 81% yield (43 mg, 0.02 mmol). Rf =0.39
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À1.76 (brs, 2H; NH), 0.83–0.89 (m, 12H; CH3), 0.92–0.98 (m, 6H; CH3),
1.22–1.54 (m, 80H; CH2), 1.69 (m, 4H; CH2), 1.90 (m, 8H; CH2), 2.00
(m, 4H; CH2), 3.81 (s, 3H; OCH3), 3.95 (s, 3H; OCH3), 4.11 (t, J=
6.4 Hz, 8H; OCH2), 4.31 (t, J=6.4 Hz, 4H; OCH2), 6.95 (d, J=8.5 Hz,
2H; ArH), 7.12 (d, J=8.5 Hz, 2H; ArH), 7.33 (s, 2H; ArH), 7.34 (s, 2H;
ArH), 7.75 (d, J=8.5 Hz, 2H; ArH), 7.96 (d, J=8.5 Hz, 2H; ArH), 8.85
(d, J=5.0 Hz, 2H; b-H), 8.99 (d, J=4.5 Hz, 4H; b-H), 9.64 ppm (d, J=
5.0 Hz, 2H; b-H); UV/Vis (CCl4): lmax (e)=446 (249100), 347 (29900),
5,15-Bis-(3,4,5-trisdecyloxyphenyl)-10,20-bis-(hexyne)-porphyrin (14)
The product was obtained in 63% yield (39 mg, 0.03 mmol). Rf =0.48
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À2.17 (brs, 2H; NH), 0.82–0.90 (m, 12H; CH3), 0.92–0.98 (m, 6H; CH3),
1.22–1.54 (m, 94H; CH2), 1.69 (m, 4H; CH2), 1.90 (m, 8H; CH2), 2.00
1892
www.chemasianj.org
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2012, 7, 1887 – 1894

Synthesis of meso-Substituted Phenylethynyl Porphyrins
581 (17100), 688 nm (12100 molÀ1 dm3 cmÀ1); LRMS (FD): m/z calcd for
C116H154N8O8: 1788.52; found: 1788.0 (the isotope profiles matched); ele-
mental analysis calcd (%) for C116H154N8O8: C 77.90, H 8.68, N 6.26;
found: C 77.86, H 8.57, N 6.17.
440 (153700), 576 (12200), 527 (10400), 683 nm (6700 molÀ1 dm3 cmÀ1);
LRMS (FD): m/z calcd for C116H148F6N8O6: 1864.51; found: 1864.8 (the
isotope profiles matched); elemental analysis calcd (%) for
C116H148F6N8O6: C 74.73, H 8.00, N 6.01; found: C 74.36, H 8.15, N 5.88.
5,15-Bis-(3,4,5-trisdecyloxyphenyl)-10-(4-ethynyl-N,N-dimethylaniline)-20-
{(4-ethynyl-N,N-dimethylaniline)- 1,1-dicyano-3-[4-
(dicyanomethylene)cyclohexa-2,5-dienylidene)}-porphyrin (26)
5,15-Dimesityl-10-(4-methoxyphenylethynyl)-20-{(4-
methoxyphenylethynyl)-1,3-diene-1,1,4,4-tetracarbonitrile)}-porphyrin (22)
The product was obtained in 80% yield (22 mg, 0.02 mmol). Rf =0.40
(hexanes/CH2Cl2, 2:3); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À1.64 (brs, 2H; NH), 1.80 (s, 6H; CH3), 1.90 (s, 6H; CH3), 2.64 (s, 6H;
CH3), 3.67 (s, 3H; OCH3), 3.94 (s, 3H; OCH3), 6.73 (d, J=8.5 Hz, 2H;
ArH), 6.09 (d, J=8.5 Hz, 2H; ArH), 7.28 (s, 2H; ArH), 7.31 (s, 2H;
ArH), 7.50 (d, J=8.5 Hz, 2H; ArH), 7.94 (d, J=8.5 Hz, 2H; ArH), 8.65
(d, J=5.0 Hz, 2H; b-H), 8.71 (d, J=4.5 Hz, 2H; b-H), 8.93 (d, J=4.5 Hz,
2H; b-H), 9.59 ppm (d, J=5.0 Hz, 2H; b-H); UV/Vis (CCl4): lmax (e)=
442 (165500), 580 (12600), 685 nm (9900 molÀ1 dm3 cmÀ1); HRMS (FD):
m/z calcd for C62H46N8O2: 934.3744; found: 934.3730 (the isotope profiles
matched).
The product was obtained in 36% yield (20 mg, 0.01 mmol). Rf =0.37
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À1.48 (brs, 2H; NH), 0.83–0.89 (m, 12H; CH3), 0.92–0.98 (m, 6H; CH3),
1.22–1.54 (m, 80H; CH2), 1.69 (m, 4H; CH2), 1.90 (m, 8H; CH2), 2.00
(m, 4H; CH2), 2.94 (s, 3H; NCH3), 3.13 (s, 3H; NCH3), 4.10–4.12 (m,
8H; OCH2), 4.30 (t, J=6.4 Hz, 4H; OCH2), 6.33 (dd, J=1.8, 7.8 Hz, 1H;
CH), 6.47 (d, J=9.0 Hz, 2H; ArH), 6.84 (d, J=9.0 Hz, 2H; ArH), 6.88
(dd, J=1.8, 7.8 Hz, 1H; CH), 7.34 (s, 2H; ArH), 7.39 (s, 2H; ArH), 7.41
(dd, J=1.8, 7.8 Hz, 1H; CH), 7.65 (dd, J=1.8, 7.8 Hz, 1H; CH), 7.66 (d,
J=9.0 Hz, 2H; ArH), 7.88 (d, J=9.0 Hz, 2H; ArH), 8.81–8.86 (m, 4H;
ArH), 9.62 ppm (d, J=5.0 Hz, 2H; ArH); UV/Vis (CCl4): lmax (e)=463
(127900), 603 (30800), 843 nm (1900 molÀ1 dm3 cmÀ1); LRMS (FD): m/z
calcd for C124H164N10O6: 1890.69; found: 1890.4 (the isotope profiles
matched).
5,15-Bis-(3,4,5-trisundecyloxyphenyl)-10-(2-ethynyl-6-
methoxynaphthalene)-20-{(2-ethynyl-6-methoxynaphthalene)-1,3-diene-
1,1,4,4-tetracarbonitrile)}-porphyrin (23)
The product was obtained in 86% yield (51 mg, 0.03 mmol). Rf =0.41
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À1.81 (brs, 2H; NH), 0.84–0.86 (m, 12H; CH3), 0.87–0.91 (m, 6H; CH3),
1.28–1.31 (m, 80H; CH2), 1.35–1.40 (m, 12H; CH2), 1.62–1.68 (m, 4H;
CH2), 1.85–1.91 (m, 8H; CH2), 1.98–2.03 (m, 4H; CH2), 3.86 (s, 3H;
OCH3), 3.97 (s, 3H; OCH3), 4.13 (t, J=6.5 Hz, 8H; CH2), 4.32 (t, J=
6.5 Hz, 4H; CH2), 7.01 (s, 1H; ArH), 7.13 (d, J=9.5 Hz, 1H; ArH), 7.20
(d, J=9.5 Hz, 1H; ArH), 7.25 (d, J=9.5 Hz, 1H; ArH), 7.44 (s, 2H;
ArH), 7.45 (s, 2H; ArH), 7.59 (d, J=9.0 Hz, 2H; ArH), 7.65 (m, 2H;
ArH), 7.89 (d, J=9.5 Hz, 1H; ArH), 8.01 (d, J=9.5 Hz, 1H; ArH), 8.18
(s, 1H; ArH), 8.45 (s, 1H; ArH), 8.92 (d, J=5.0 Hz, 2H; b-H), 9.01 (d,
J=5.0 Hz, 2H; b-H), 9.04 (d, J=5.0 Hz, 2H; b-H), 9.73 ppm (d, J=
5.0 Hz, 2H; b-H); UV/Vis (CCl4): lmax (e)=449 (189300), 585 (18000),
689 nm (11200 molÀ1 dm3 cmÀ1); LRMS (FD): m/z calcd for C130H170N8O8:
1972.80; found: 1972.0 (the isotope profiles matched); elemental analysis
calcd (%) for C130H170N8O8: C 79.15, H 8.69, N 5.68; found: C 78.93,
H 8.51, N 5.62.
5,15-Bis-(3,4,5-trisdecyloxyphenyl)-10-(4-methoxyphenylethynyl)-20-{(4-
methoxyphenylethynyl)-1,1-dicyano-3-[4-(dicyanomethylene)cyclohexa-
2,5-dienylidene)}-porphyrin (27)
The product was obtained in 86% yield (48 mg, 0.03 mmol). Rf =0.39
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À1.98 (brs, 2H; NH), 0.83–0.89 (m, 12H; CH3), 0.92–0.98 (m, 6H; CH3),
1.22–1.54 (m, 80H; CH2), 1.69 (m, 4H; CH2), 1.90 (m, 8H; CH2), 2.00
(m, 4H; CH2), 3.48 (s, 3H; OCH3), 3.96 (s, 3H; OCH3), 4.08 (t, J=
6.4 Hz, 4H; OCH2), 4.14 (t, J=6.4 Hz, 4H; OCH2), 4.29 (t, J=6.4 Hz,
4H; OCH2), 6.48 (d, J=8.5 Hz, 2H; ArH), 6.50 (dd, J=1.8, 7.8 Hz, 1H;
CH), 6.93 (dd, J=1.8, 7.8 Hz, 1H; CH), 7.11 (d, J=8.5 Hz, 2H; ArH),
7.31 (s, 2H; ArH), 7.39 (s, 2H; ArH), 7.49 (d, J=8.5 Hz, 2H; ArH), 7.60
(dd, J=1.8, 7.8 Hz, 1H; CH), 7.82 (dd, J=1.8, 7.8 Hz, 1H; CH), 7.96 (d,
J=8.5 Hz, 2H; ArH), 8.81–8.84 (m, 2H; b-H), 8.87 (d, J=4.8 Hz, 2H; b-
H), 8.90 (d, J=4.8 Hz, 2H; b-H), 9.63 ppm (d, J=5.0 Hz, 2H; b-H); UV/
Vis (CCl4): lmax (e)=451 (248000), 584 (30000), 822 nm
(1600 molÀ1 dm3 cmÀ1); LRMS (FD): m/z calcd for C122H158N8O8: 1864.60;
found: 1864.1 (the isotope profiles matched).
5,15-Bis-(3,4,5-trisdecyloxyphenyl)-10-(phenylethynyl)-20-
{(phenylethynyl)-1,3-diene-1,1,4,4-tetracarbonitrile)}-porphyrin (24)
5,15-Bis-(3,4,5-trisdecyloxyphenyl)-10-(phenylethynyl)-20-
{(phenylethynyl)-1,1-dicyano-3-[4-(dicyanomethylene)cyclohexa-2,5-
dienylidene)}-porphyrin (28)
The product was obtained in 83% yield (43 mg, 0.02 mmol). Rf =0.39
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À2.05 (brs, 2H; NH), 0.83–0.89 (m, 12H; CH3), 0.92–0.98 (m, 6H; CH3),
1.22–1.54 (m, 80H; CH2), 1.69 (m, 4H; CH2), 1.90 (m, 8H; CH2), 2.00
(m, 4H; CH2), 4.12 (t, J=6.4 Hz, 8H; OCH2), 4.32 (t, J=6.4 Hz, 4H;
OCH2), 7.19–7.21 (m, 4H; ArH), 7.32–7.40 (m, 6H; ArH), 7.59–7.60 (m,
2H; ArH), 8.02–8.05 (m, 2H; ArH), 8.94 (d, J=5.0 Hz, 2H; b-H), 9.01
(d, J=4.5 Hz, 4H; b-H), 9.69 ppm (d, J=5.0 Hz, 2H; b-H); UV/Vis
The product was obtained in 80% yield (43 mg, 0.02 mmol). Rf =0.40
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À2.18 (brs, 2H; NH), 0.83–0.89 (m, 12H; CH3), 0.92–0.98 (m, 6H; CH3),
1.22–1.54 (m, 80H; CH2), 1.69 (m, 4H; CH2), 1.90 (m, 8H; CH2), 2.00
(m, 4H; CH2), 4.08 (t, J=6.4 Hz, 4H; OCH2), 4.15 (t, J=6.4 Hz, 4H;
OCH2), 4.30 (t, J=6.4 Hz, 4H; OCH2), 6.55 (dd, J=1.8, 7.8 Hz, 1H;
CH), 6.94 (dd, J=1.8, 7.8 Hz, 1H; CH), 7.31 (s, 2H; ArH), 7.32–7.40 (m,
6H; ArH), 7.41 (s, 2H; ArH), 7.59–7.60 (m, 2H; ArH), 7.66 (dd, J=1.8,
7.8 Hz, 1H; CH), 7.93 (dd, J=1.8, 7.8 Hz, 1H; CH), 8.02–8.05 (m, 2H;
ArH), 8.70–8.88 (m, J=4.8 Hz, 2H; b-H), 8.89–8.98 (m, 4H; b-H),
9.67 ppm (d, J=5.0 Hz, 2H; b-H); UV/Vis (CCl4): lmax (e)=447
(226000), 578 (26000), 780 nm (1000 molÀ1 dm3 cmÀ1); LRMS (FD): m/z
(CCl4):
lmax
(e)=441
(221400),
579
(14400),
682 nm
(8600 molÀ1 dm3 cmÀ1); LRMS (FD): m/z calcd for C114H150N8O6: 1728.52;
found: 1728.0 (the isotope profiles matched); elemental analysis calcd
(%) for C114H150N8O6: C 79.22, H 8.75, N 6.48; found: C 79.03, H 8.83,
N 6.32.
15-Bis-(3,4,5-trisdecyloxyphenyl)-10-(4-trifluoromethylphenylethynyl)-20-
{(4-trifluoromethylphenylethynyl)-1,3-diene-1,1,4,4-tetracarbonitrile)}-
porphyrin (25)
calcd for
matched).
C
120H154N8O6: 1804.55; found: 1804.0 (the isotope profiles
The product was obtained in 98% yield (55 mg, 0.03 mmol). Rf =0.37
(hexanes/EtOAc, 95:5); 1H NMR (500 MHz, CDCl3, 258C, TMS): d=
À2.22 (brs, 2H; NH), 0.83–0.89 (m, 12H; CH3), 0.92–0.98 (m, 6H; CH3),
1.22–1.54 (m, 80H; CH2), 1.69 (m, 4H; CH2), 1.90 (m, 8H; CH2), 2.00
(m, 4H; CH2), 4.12 (t, J=6.4 Hz, 8H; OCH2), 4.32 (t, J=6.4 Hz, 4H;
OCH2), 7.11 (d, J=7.2 Hz, 2H; ArH), 7.23 (d, J=7.2 Hz, 2H; ArH), 7.35
(s, 2H; ArH), 7.37 (s, 2H; ArH), 7.85 (d, J=7.5 Hz, 2H; ArH), 8.14 (d,
J=8.5 Hz, 2H; ArH), 8.89 (d, J=5.0 Hz, 2H; b-H), 9.02 (d, J=4.5 Hz,
4H; b-H), 9.68 ppm (d, J=5.0 Hz, 2H; b-H); UV/Vis (CCl4): lmax (e)=
Acknowledgements
Financial support of our work from the Foundation for Polish Science
(Grant No. TEAM/2009-4/3) is gratefully acknowledged. We thank Eva
Nichols (Caltech) for amending the manuscript.
Chem. Asian J. 2012, 7, 1887 – 1894
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
1893

Daniel T. Gryko et al.
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Received: February 25, 2012
Published online: May 23, 2012
1894
www.chemasianj.org
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2012, 7, 1887 – 1894