Bisthiophene-Substituted Zinc(II) Phthalocyanines
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found: 983.7823; elemental analysis calcd (%) for C33H15I3N8OZn: C
40.21, H 1.53, N 11.37; found: C, 40.38, H 1.67, N 11.16.
2-Formyl-9(10),16(17),23(24)-triiodophthalocyaninato zinc(II) (mixture
of regioisomers) (5): A solution of IBX (128 mg, 0.45 mmol) in DMSO
(5 mL) was added to a stirred solution of Pc 4 (90 mg, 0.09 mmol) in
THF (2 mL) in an argon atmosphere. The mixture was stirred at room
temperature for 24 h. The reaction was monitored by TLC (toluene/THF,
10:1 v/v) until all the starting Pc had reacted. Brine was then added and
the mixture was extracted with THF. The combined organic layers were
dried over MgSO4 and evaporated in vacuo. The solid residue was puri-
fied by column chromatography on silica gel (toluene/THF, 10:1 v/v) to
give 57 mg (64%) of 5. 1H NMR (300 MHz, [D8]THF, 258C, TMS): d=
10.85 (s, 1H, CHO), 9.67–9.31 (m, 4H), 9.30–9.05 (m, 1H), 8.94–8.68 (m,
4H), 8.67–8.44 ppm (m, 3H); IR (KBr): n˜ =2954, 2923, 2854, 1691, 1594,
1484, 1456, 1431, 1378, 1304, 1139, 1091, 1053, 1033, 894, 755 cmÀ1; UV/
Vis (THF): lmax (log e)=673 (5.19), 653 (sh) (4.48), 608 (sh) (4.46),
354 nm (4.76); MS (MALDI, dithranol): m/z: 981.8 [M]+; HRMS
(MALDI-TOF, dithranol): m/z: calcd for C33H13I3N8OZn [M]+: 981.7638;
found: 981.7603; elemental analysis calcd (%) for C33H13I3N8OZn: C
40.30, H 1.33, N 11.39; found: C 40.52, H 1.62, N 11.08.
2-Carboxy-9(10),16(17),23(24)-triiodophthalocyaninato zinc(II) (mixture
of regioisomers) (3): A solution of H3NO3S (9.7 mg, 0.1 mmol) in H2O
(1 mL) was added to a solution of phthalocyanine 5 (25 mg, 0.025 mmol)
in THF (3 mL), at 08C. A solution of NaClO2 (4.6 mg, 0.050 mmol) in
H2O (1 mL) was added dropwise while the temperature was kept at 08C.
After the addition was complete, the mixture was further stirred for a 1 h
at room temperature. Brine was then added and the mixture was extract-
ed with THF. The combined organic layers were dried over MgSO4 and
evaporated in vacuo. The solid residue was purified by short column
chromatography on silica gel (THF) to give 15 mg (60%) of 3. 1H NMR
(300 MHz, [D8]THF, 258C, TMS): d=9.93–9.68 (m, 1H), 9.58–9.30 (m,
3H), 9.27–9.08 (m, 1H), 9.02–8.70 (m, 4H), 8.63–8.43 ppm (m, 3H); IR
(KBr): n˜ =3437, 2953, 2922, 2857, 1687, 1612, 1454, 1383, 1305, 1264,
1140, 1096, 1045, 923, 887, 812, 747 cmÀ1; UV/Vis (THF): lmax (log e)=
675 (4.97), 641 (sh) (4.48), 611 (sh) (4.41), 349 nm (4.70); MS (MALDI,
dithranol): m/z: 997.8 [M]+; HRMS (MALDI-TOF, dithranol): m/z:
calcd for C33H13I3N8O2Zn [M]+: 997.7587; found: 997.7589; elemental
analysis calcd (%) for C33H13I3N8O2Zn: C 39.65, H 1.31, N 11.21; found:
C 39.99, H 1.60, N 11.02.
Figure 4. IPCE spectrum and I–V curves for devices of 1- and 2-sensitized
solar cells. The cells were the same as those in Table 3.
2-Carboxy-9(10),16(17),23(24)-tris-[2-(N,N-bis-(9,9-dimethylfluoren-2-yl)-
4-aminophenyl)-5,5’-bithiophene]phthalocyaninato zinc(II) (mixture of
regioisomers) (1): A suspension of ZnPc 3 (33 mg, 0.033 mmol), bisthio-
pheneboronic acid pinacol ester
4 (102 mg, 0.13 mmol), [PdACHTUNGTRENNUNG(PPh3)4]
(3.5 mg, 0.003 mmol), and a solution of Na2CO3 (34 mg, 0.33 mmol) in
H2O (1 mL) in DME (5 mL) was stirred at 958C in an argon atmosphere
for 24 h. The suspension was then cooled to room temperature and
poured into a 1m NH4Cl solution (50 mL). The mixture was extracted
with ethyl acetate (2ꢆ50 mL) and the combined organic extracts were
washed with brine (10 mL), dried over MgSO4 and evaporated in vacuo.
The crude product was purified by preparative size-exclusion chromatog-
raphy (Biobeads SX-1 in THF) to yield 30 mg (36%) of a dark-green
solid. 1H NMR (300 MHz, [D8]THF, 258C, TMS): d=10.41–6.32 (m,
78H, ArH), 1.82–0.92 ppm (m, 36H, alkylH); IR (KBr): n˜ =3435, 2957,
2920, 2860, 1724, 1604, 1535, 1488, 1452, 1390, 1308, 1183, 1141, 1055,
822, 789 cmÀ1; UV/Vis (THF): lmax (log e)=707 (4.78), 662 (4.58), 413
(4.87), 369 nm (4.98); MS (MALDI, DCTB): m/z: 2537.7 [M]+; HRMS
(MALDI, DCTB): m/z: calcd for C165H115N11O2S6Zn [M]+: 2537.685;
found: 2537.695.
tuted carboxy–ZnPc dyes by this method, in which aggrega-
tion phenomena are suppressed.
Experimental Section
2-Hydroxymethyl-9(10),16(17),23(24)-triiodophthalocyaninato
(mixture of regioisomers) (4):
mixture of 4-iodophthalonitrile[16]
(525 mg, 2.07 mmol), (64 mg,
4-(hydroxymethyl)phthalonitrile[17]
0.41 mmol), and Zn(OAc)2 (121 mg, 0.66 mmol) in DMAE (6 mL) was
zinc(II)
A
ACHTUNGTRENNUNG
heated at reflux and stirred for 20 h in an argon atmosphere. After cool-
ing to room temperature, the solvent was removed and the residue was
washed with a MeOH/H2O (5:1, v/v) mixture. The crude product was pu-
rified by column chromatography on silica gel. A toluene/THF (10:1, v/v)
eluent removed most of the symmetric tetraiodo Pc,[14] and a second
column in hexane/dioxane (3:2, v/v) was necessary to completely purify
2-Carboxy-9(10),16(17),23(24)-tris[5’-hexyl-2,2’-bithiophene]phthalocya-
ninato zinc(II) (mixture of regioisomers) (2): ZnPc 2 was prepared as
compound 1, by using ZnPc 3 (20 mg, 0.02 mmol), 5’-hexyl-2,2’-bithio-
1
phene-5-boronic acid pinacol ester (7) (22.5 mg, 0.06 mmol), [PdACHTUNGTRENNUNG(PPh3)4]
Pc 4. Yield: 93 mg, 23%. H NMR (300 MHz, [D8]THF, 258C, TMS): d=
(2.3 mg, 0.002 mmol), and Na2CO3 (1 mL of a 1m aqueous solution). The
9.46–9.33 (m, 3H), 9.18–8.98 (m, 2H), 8.95–8.67 (m, 3H), 8.66–8.39 (m,
3H), 8.36–8.17 (m, 1H), 5.46 (s, 2H), 5.1–4.90 ppm (br, 1H); IR (KBr):
n˜ =3503, 2957, 2922, 2401, 1603, 1589, 1381, 1304, 1264, 1140, 1097, 1057,
901, 816, 741 cmÀ1; UV/Vis (THF): lmax (log e)=673 (5.08), 608 (sh)
(4.37), 357 nm (4.69); MS (MALDI, dithranol): m/z: 983.8 [M]+; HRMS
(MALDI-TOF, dithranol): m/z: calcd for C33H15I3N8OZn [M]+: 983.7794;
crude product was purified by preparative size-exclusion chromatography
1
(Biobeads SX-1 in THF) to yield 12 mg (43%) of a green solid. H NMR
(300 MHz, [D8]THF, 258C, TMS): d=10.34–6.36 (several m, 24H, ArH),
1.82–0.92 ppm (m, 39H, alkyl); IR (KBr): n˜ =3432, 2954, 2923, 2853,
1656, 1608, 1491, 1455, 1380, 1337, 1285, 1261, 1144, 1096, 1049, 1026,
Chem. Eur. J. 2012, 18, 6343 – 6348
ꢄ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6347