New dual donor-acceptor (2D-π-2A) porphyrin sensitizers for stable and cost-effective dye-sensitized solar cells

Article abstract of DOI:10.1002/asia.201300328

A series of porphyrin sensitizers that featured two electron-donating groups and dual anchoring groups that were connected through a porphine π-bridging unit have been synthesized and successfully applied in dye-sensitized solar cells (DSSCs). The presence of electron-donating groups had a significant influence on their spectroscopic, electrochemical, and photovoltaic properties. Overall, the dual anchoring groups gave tunable electronic properties and stronger attachment to TiO₂. These new dyes were readily synthesized in a minimum number of steps in gram-scale quantities. Optical and electrochemical data confirmed the advantages of these dyes for use as sensitizers in DSSCs. Porphyrins with electron-donating amino moieties provided improved charge separation and better charge-injection efficiencies for the studied dual-push-pull dyes. Attenuated total reflectance-Fourier-transform infrared (ATR-FTIR) and X-ray photoelectron spectroscopy of the porphyrin dyes on TiO₂ suggest that both p-carboxyphenyl groups are attached onto TiO₂, thereby resulting in strong attachment. Among these dyes, cis-Zn2BC2A, with two electron-donating 3,6-ditertbutyl-phenyl-carbazole groups and dual-anchoring p-carboxyphenyl groups, showed the highest efficiency of 4.07 %, with J_SC=9.81 mA cm^-2, V_OC=0.63 V, and FF=66 %. Our results also indicated a better photostability of the studied dual-anchored sensitizers compared to their mono-anchored analogues under identical conditions. These results provide insight into the developments of a new generation of high-efficiency and thermally stable porphyrin sensitizers. Pull the other one: Porphyrin sensitizers with two electron-donating and dual anchoring groups were successfully applied in dye-sensitized solar cells. A highest efficiency of 4.07 % was achieved by using cis-Zn2BC2A as the sensitizer. Copyright

Full text of DOI:10.1002/asia.201300328

Supporting Information
ꢀ Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013
New Dual Donor–Acceptor (2D-p-2A) Porphyrin Sensitizers for Stable and
Cost-Effective Dye-Sensitized Solar Cells
Ram B. Ambre,[a] Gao-Fong Chang,[a] Manoj R. Zanwar,[b] Ching-Fa Yao,[b]
Eric Wei-Guang Diau,*[c] and Chen-Hsiung Hung*[a]
asia_201300328_sm_miscellaneous_information.pdf

Supporting information
Novel Dual Donor-Acceptor (2D-π-2A) Porphyrin Sensitizers for
Stable and Cost-Effective Dye-Sensitized Solar Cells
Table of contents
1. Figure S1: The ATR-FTIR of neat porphyrins contrasted with porphyrins on TiO2 of
cis-Zn2T2A, cis-Zn2TH2A cis-Zn2TC2A, and cis-Zn2BC2A.…………………………
02
2. Synthesis and characterization data of 2D-π-2A porphyrin sensitizers……………….
3. Synthesis and characterization data of Zn1TPA3A…………………………………...
4. NMR and HR-MS of cis-2T2E, cis-2U2E, cis-2TH2E, cis-2TC2E, cis-2BC2E, and
cis-2TPA2E………………………………………………………………………………
5. NMR and HR-MS of cis-Zn2T2E, cis-Zn2U2E, cis-Zn2TH2E, cis-Zn2TC2E,
cis-Zn2BC2E, and cis-Zn2TPA2E……………………………………………………….
6. NMR and HR-MS of cis-Zn2T2A, cis-Zn2U2A, cis-Zn2TH2A, cis-Zn2TC2A,
cis-Zn2BC2A, and cis-Zn2TPA2A………………………………………………………
7. NMR and HR-MS of 3TPA1E, Zn3TPA1E, and Zn3TPA1A…………………………
02-10
10-11
12-17
18-23
24-29
30-32
1

Figure S1. The comparative ATR-FTIR of neat porphyrin samples contrasted with porphyrins on
TiO2 of (a) cis-Zn2T2A and cis-Zn2T2A/TiO2, (b) cis-Zn2BC2A and cis-Zn2BC2A/TiO2, (c) cis-
Zn2TH2A and cis-Zn2TH2A/TiO2, and (d) cis-Zn2TC2A and cis-Zn2TC2A/TiO2.
Synthesis of 2D-π-2A porphyrin sensitizers
(I) Mixed condensation. In a 1000 ml round bottom flask equipped with a magnetic stirrer,
nitrogen inlet and outlet, CH2Cl2 (750 ml) was added and purged with nitrogen gas for 10 min.
Pyrrole (0.500 g, 7.5 mmol), methyl 4-formylbenzoate (0.615 g, 3.75 mmol), and the required
carboxyaldehyde (3.75 mmol) were added and degassed. Then, 48% boron trifluoride-diethyl
ether (10 mol%, 0.142 mL) was added. The reaction mixture was protected from light. After
stirred at room temperature for 1 h, DDQ (1.70 g, 7.5 mmol) was added and the solution was
continuously stirred at room temperature for another 1 h in open atmosphere. Excess
dichloromethane was removed completely on a rotary evaporator. The dark powder dissolved in
minimum amount of CH2Cl2 was eluted through short silica gel column with 2% methanol in
2

dichloromethane as the eluent. The porphyrin fraction was concentrated and then separated on a
second silica gel column eluted with a solvent gradient from 7:3 (v/v) dichloromethane/hexane to
pure dichloromethane. The yields of the obtained porphyrins cis-2T2E, cis-2U2E, cis-2TH2E,
cis-2TC2E, cis-2BC2E, or cis-2TPA2E are reported in Table S1.
a
Table
S1.
Mixed condensation
R
R
N
COOMe
CHO
OEt2
,
(i)BF3.
NH
HN
other 5
porphyrins
(iI)DDQ
+
+
+
R
CHO
N
N
CH2Cl2
H
MeOOC
COOMe
cis-2X2E
Yield(%)b
2.69
Yield(%)b
2.51
R
cis-2X2E
cis-2T2E
R
cis-2X2E
tBu
N
N
cis-2TC2E
S
tBu
tBu
cis-2U2E
C11
H23
cis-2BC2E
1.44
0.82
4.26
1.86
tBu
cis-2TH2E
cis-2TPA2E
N
H13
C6
S
aReaction conditions: (i) methyl 4-formylbenzoate (3.75 mmol), required-carboxyaldehyde (3.75 mmol),
pyrrole (7.5 mmol), BF3.OEt2 (10 mol%), CH2Cl2 (750 mL), 1 h (ii) DDQ (7.5 mmol), 1 h. b Yields of
analytically pure product.
(II) Zinc metalation. The respective free base porphyrin cis-2T2E, cis-2U2E, cis-2TH2E, cis-
2TC2E, cis-2BC2E, or cis-2TPA2E (60 mg) was dissolved in 30 ml dichloromethane. To this
solution Zn(OAc)2·2H2O (1.5 equivalent) dissolved in 10 mL methanol was added. Reaction
mixture was refluxed for 1 h. Reaction progress was monitored by TLC and UV‒visible
spectroscopy. The solution was concentrated under reduced pressure and purified directly by
silica gel column chromatography eluted with dichloromethane to give zinc porphyrins cis-
3

Zn2T2E, cis-Zn2U2E, cis-Zn2TH2E, cis-Zn2TC2E, cis-Zn2BC2E, or cis-Zn2TPA2E The yields
of the reactions are reported in Table S2.
a
Table
S2.
Zinc metalation
R
R
R
R
N
N
N
Zn
N
.2H
2O
Zn(OAc)2
NH
HN
N
N
CH2Cl2/MeOH
CO2Me
MeO2C
CO2
Me
MeO2C
cis
-Zn2X2E
Yield(%)b
Yield(%)b
92
R
cis-Zn2X2E
cis-Zn2T2E
cis-Zn2X2E
tBu
Product
N
cis-Zn2TC2E
74
98
99
S
tBu
tBu
cis-Zn2U2E
cis-Zn2BC2E
cis-Zn2TPA2E
H23
C11
91
99
N
tBu
cis-Zn2TH2E
N
H13
C6
S
a Reaction conditions: free base porphyrin (60 mg), Zn(OAc)2·2H2O (1.5 equivalent), CH2Cl2/MeOH
(3/1, v/v), reflux 1 h, b Yield of analytically pure products.
(III) Hydrolysis. The respective zinc porphyrin cis-Zn2T2E, cis-Zn2U2E, cis-Zn2TH2E,
cis-Zn2TC2E, cis-Zn2BC2E, or cis-Zn2TPA2E (50 mg) was dissolved in 40 ml solvent
(THF/MeOH, V/V, 3/1), to this solution 20 equivalent of 1 M aqueous KOH was
added and refluxed for 10 h. After cooling, the reaction mixture was treated slowly
with 0.1 M HCl. The precipitation formed was filtered off and washed with distilled
water. The residue remained was dried on vacuum to yield analytically pure cis-
4

Zn2T2A, cis-Zn2U2A, cis-Zn2TH2A, cis-Zn2TC2A, cis-Zn2BC2A, and cis-Zn2TPA2A in
good yields as reported in Table S3.
a
Table
S3.
Hydrolysis
R
R
R
R
N
Zn
N
N
Zn
N
KOH
N
N
N
N
THF
/MeOH
H
CO2
CO2Me
HO2C
MeO2C
cis
-Zn2X2A
Yield(%)b
Yield(%)b
90
R
cis-Zn2X2A
R
cis-Zn2X2A
tBu
N
cis-Zn2TC2A
cis-Zn2T2A
99
S
tBu
tBu
cis-Zn2BC2A
cis-Zn2TPA2A
cis-Zn2U2A
H23
C11
99
89
93
98
N
tBu
cis-Zn2TH2A
N
H13
C6
S
a Reaction conditions: zinc porphyrin (50 mg), KOH (20 equiv., 1 M), THF/MeOH (3/1, v/v),
reflux, 10 h. b Yields of analytically pure products.
Characterization data
5,10-bis(4-methoxycarbonylphenyl)15,20-bis(4-methylphenyl)porphyrin (cis-2T2E). mp ˃
300 oC; 1H NMR (300 MHz, CDCl3) δ = 8.90-8.88 (m, 4H), 8.80-8.77 (m, 4H), 8.44 (d, J = 803
Hz, 4H), 8.30 (d, J = 8.3 Hz, 4H ), 8.09 (d, J = 7.7 Hz, 4H), 7.56 (d, J = 7.7 Hz, 4H), 4.11 (s,
6H), 2.71 (s, 6H), -2.70 (s, 2H); IR (Neat, cm-1): 3314, 1725, 1606, 1433, 1270, 1181, 1109,
1099, 1070, 1021, 995, 982, 796, 759; λabs/nm (CH2Cl2): 420, 516, 554, 588, 646; HRMS-ESI
calcd for C50H38N4O4 ([M+H]+): 759.2971, found 759.2979.
5

o
5,10-bis(4-methoxycarbonylphenyl)15,20-bis(undecyl)porphyrin (cis-2U2E). mp ˃ 300 C;
1H NMR (300 MHz, CDCl3) δ = 9.57 (s, 2H), 9.46 (d, J = 8.7 Hz, 2H), 8.80 (d, J = 4.6 Hz, 2H ),
8.69 (s, 2H), 8.42 (d, J = 8.0 Hz, 4H), 8.25 (d, J = 7.9 Hz, 4H ) 4.99 (t, J = 7.8 Hz, 4H), 4.12 (s,
6H), 2.55 (p, J = 7.8 Hz, 4H) 1.81 (p, J = 7.8 Hz, 4H), 1.81 (p, J = 7.3 Hz, 4H), 1.37-1.26 (m, 24
H), 0.87 (t, J = 6.9 Hz, 6H), -2.70 (s, 2H; IR (Neat, cm-1): 3319, 1721, 1607, 1434, 1272, 1177,
1110, 1099, 1021, 963, 792; λabs/nm (CH2Cl2): 418, 518, 554, 596, 650; HRMS-ESI calcd for
C58H70N4O4 ([M+H]+): 887.5475, found 887.5480.
5,10-bis(4-methoxycarbonylphenyl)15,20-bis(4-hexyl-2-thienyl)porphyrin (cis-2TH2E). mp
˃ 300 oC; 1H NMR (400 MHz, CDCl3) δ = 9.16-9.15 (m, 4H), 8.80-8.78 (m, 4H), 8.46 (d, J = 8.3
Hz, 4H), 8.31 (d, J = 8.6 Hz, 4H ), 7.72 (d, J = 3.7 Hz, 2H), 7.19 (d, J = 2.8 Hz, 2H), 4.13 (s,
6H), 3.15 (t, J = 7.5 Hz, 4H), 1.98 (p, J = 7.6 Hz, 4H), 1.64-1.58 (m, 4 H), 1.50-1.42 (m, 8H),
0.99 (t, J = 6.4 Hz, 6H), -2.66 (s, 2H); IR (Neat, cm-1): 3319, 1724, 1608, 1467, 1435, 1275,
1177, 1112, 978, 964, 848; λabs/nm (CH2Cl2): 426, 520, 558, 596, 654; HRMS-ESI calcd for
C58H62N4O2S3 ([M+H]+): 911.3665, found 911.3677.
5,10-bis(4-methoxycarbonylphenyl)15,20-bis(3,6-di-tert-butyl-9-(thiophen-2-yl)-9H-
carbazole)porphyrin (cis-2TC2E). mp ˃ 300 oC; 1H NMR (400 MHz, CDCl3) δ = 9.37 (s, 2H),
9.29 (d, J = 4.7 Hz, 2H), 8.88 (d, J = 4.7 Hz, 2H), 8.80 (s, 2H), 8.47 (d, J = 8.1 Hz, 4H), 8.32 (d,
J= 8.1 Hz, 4H), 8.21 (d, J= 1.7 Hz, 4H), 7.99 (d, J = 3.5 Hz, 2H ), 7.86 (d, J = 8.5 Hz, 4H ),
7.68-7.65 (m, 4H), 7.63 (d, J = 3.5 Hz, 2H), 4.13 (s, 6H), 1.55 (s, 36H), -2.62 (s, 2H); IR (Neat,
cm-1): 3317, 1722, 1606, 1588, 1550, 1483, 1361, 1274, 1263, 1178, 1110, 975, 800, 763, 750;
λabs/nm (CH2Cl2): 424, 521, 559, 593, 652; HRMS-ESI calcd for C84H76N6O4S2 ([M+H]+):
1297.5448, found 1297.5487.
5,10-bis(4-methoxycarbonylphenyl)15,20-bis(3,6-di-tert-butyl-9-phenyl-9H-
carbazole)porphyrin (cis-2BC2E). mp ˃ 300 oC; 1H NMR (400 MHz, CDCl3) δ = 9.10 (s, 2H),
9.07 (d, J = 4.7 Hz, 2H), 8.90 (d, J = 4.7 Hz, 2H), 8.86 (s, 2H), 8.49-8.45 (m, 8H), 8.35 (d, J =
7.9 Hz, 4H ), 8.27 (s, 4H), 8.02 (d, J = 8.1 Hz, 4H), 7.80 (d, J=8.6 Hz, 4H), 7.65 (d, J=8.6 Hz,
4H), 4.13 (s, 6H), 1.55 (s, 36H), -2.67 (s, 2H); IR (Neat, cm-1): 3314, 1724, 1702, 1604, 1514,
1470, 1362, 1260, 1110, 1056, 1052, 966, 796, 731; λabs/nm (CH2Cl2): 420, 513, 551, 591, 648;
HRMS-ESI calcd for C88H80N6O4 ([M+H]+): 1285.6319, found 1285.6368.
6

5,10-bis(4-methoxycarbonylphenyl)15,20-bis(4-diphenylaminophenyl)porphyrin
(cis-
2TPA2E). mp ˃ 300 oC; 1H NMR (400 MHz, CDCl3) δ = 9.03 (s, 2H), 9.02 (d, J = 3.5 Hz, 2H),
8.81 (d, J = 4.8 Hz, 2H), 8.79 (s, 2H), 8.45 (d, J = 8.0 Hz, 4H), 8.31 (d, J = 8.3 Hz, 4H ), 8.32 (d,
J = 8.3 Hz, 4H), 7.47 (d, J = 8.36 Hz, 4H), 7.43-7.42 (m, 16H), 7.17-7.13 (m, 4H), 4.12 (s, 6H), -
2.70 (s, 2H); IR (Neat, cm-1): 3031, 1720, 1605, 1588, 1523, 1486, 1401, 1268, 1110, 995, 856,
811, 794; λabs/nm (CH2Cl2): 420, 520, 562, 652, 730; HRMS-ESI calcd for C72H52N6O4
([M+H]+): 1065.4128, found 1065.4124.
5,10-bis(4-methoxycarbonylphenyl)15,20-bis(4-methylphenyl)porphyrinato zinc(II) (cis-
Zn2T2E). mp ˃ 300 oC; 1H NMR (400 MHz, CDCl3) δ = 9.00-8.98 (m, 4H), 8.89 (s, 2H), 8.87
(d, J = 5.0 Hz, 2H), 8.41 (d, J = 8.4 Hz, 4H), 8.30 (d, J = 8.1 Hz, 4H ), 8.09 (d, J = 7.7 Hz, 4H),
7.56 (d, J = 7.6Hz, 4H), 4.09 (s, 6H) 2.71 (s, 6H); IR (Neat, cm-1): 1721, 1694, 1606, 1486, 1274,
1205, 1181, 1100, 1069, 1010, 996, 794; λabs/nm (CH2Cl2): 420, 550, 590; HRMS- FAB calcd
for C50H36N4O4Zn ([M+]): 820.2028, found 820.2038.
5,10-bis(4-methoxycarbonylphenyl)15,20-bis(undecyl)porphyrinato zinc(II) (cis-Zn2U2E).
o
1
mp ˃ 300 C; H NMR (400 MHz, CDCl3) δ = 9.24 (d, J = 4.7 Hz, 2H), 8.95 (s, 2H), 8.79 (s,
2H), 8.73 (d, J = 4.6 Hz, 2H ), 8.39 (d, J = 8.0 Hz, 4H), 8.24 (d, J = 8.0 Hz, 4H ) 4.47 (t, J = 8.2
Hz, 4H), 4.08 (s, 6H), 2.32 (p, J = 7.4 Hz, 4H), 1.73 (p, J = 7.6 Hz, 4H), 1.48 (p, J = 7.6 Hz, 4H),
1.35-1.28 (m, 24 H), 0.88 (t, J = 6.9 Hz, 6H); IR (Neat, cm-1): 1722, 1697, 1606, 1435, 1271,
1111, 1100, 1075, 998, 790; λabs/nm (CH2Cl2): 420, 552, 592; HRMS- MALDI-TOF calcd for
C58H68N4O4Zn ([M+H]+): 949.4610, found 949.4620.
5,10-bis(4-methoxycarbonylphenyl)15,20-bis(4-hexyl-2-thienyl)porphyrinato zinc(II) (cis-
o
1
Zn2TH2E). mp ˃ 300 C; H NMR (400 MHz, CDCl3) δ = 9.25 (s, 2H), 9.24 (d, J = 4.6 Hz,
2H), 8.87 (d, J = 4.6 Hz, 2H), 8.85 (s, 2H ), 8.38 (d, J = 8.1 Hz, 4H), 8.27 (d, J = 8.0 Hz, 4H ),
7.70 (d, J = 3.3 Hz, 2H), 7.18 (d, J = 3.2 Hz, 2H), 4.06 (s, 6H), 3.13 (t, J = 7.6 Hz, 4H), 1.95 (p, J
= 7.5 Hz, 4H), 1.59 (p, J = 7.5, 4 H), 1.48-1.43 (m, 8H), 0.97 (t, J = 6.9 Hz, 6H); IR (Neat, cm-1):
1721, 1606, 1434, 1275, 1112, 1110, 999, 977, 793; λabs/nm (CH2Cl2): 426, 554, 596; HRMS-
MALDI-TOF calcd for C44H28N4O4S2Zn ([M+H]+): 973.2800, found 973.2811.
5,10-bis(4-methoxycarbonylphenyl)15,20-bis(3,6-di-tert-butyl-9-(thiophen-2-yl)-9H-
carbazole)porphyrinato zinc(II) (cis-Zn2TCE). mp ˃ 300 oC; 1H NMR (400 MHz, CDCl3) δ =
7

9.46 (s, 2H), 9.38 (d, J = 4.6 Hz, 2H), 8.96 (d, J = 4.6 Hz, 2H), 8.88 (s, 2H), 8.41 (d, J = 8.1 Hz,
4H), 8.32 (d, J= 8.1 Hz, 4H), 8.22 (d, J= 1.7 Hz, 4H), 7.98 (d, J = 3.6 Hz, 2H ), 7.88 (d, J = 8.6
Hz, 4H ), 7.68-7.65 (m, 4H), 7.62 (d, J = 3.6 Hz, 2H), 4.08 (s, 6H), 1.53 (s, 36H) ; IR (Neat, cm-
1): 1722, 1608, 1552, 1488, 1465, 1363, 1274, 1176, 1112, 1072, 1000, 979, 875, 792, 763, 750,
715; λabs/nm (CH2Cl2): 426, 553, 596; HRMS-ESI calcd for C84H74N6O4S2Zn ([M+H]+):
1359.4583, found 1359.4630.
5,10-bis(4-methoxycarbonylphenyl)15,20-bis(3,6-di-tert-butyl-9-phenyl-9H-
carbazole)porphyrinato zinc(II) (cis-Zn2BC2E). mp ˃ 300 oC; 1H NMR (400 MHz, CDCl3) δ
= 9.20 (s, 2H), 9.17 (d, J = 4.7 Hz, 2H), 9.00 (d, J = 4.7 Hz, 2H), 8.95 (s, 2H), 8.46 (d, J = 8.1
Hz, 4H ), 8.42 (d, J = 7.9 Hz, 4H), 8.34 (d, J=8.0 Hz, 4H), 8.27 (d, J = 1.32 Hz, 4H), 8.01 (d,
J=8.1 Hz, 4H), 7.80 (d, J=8.6 Hz, 4H), 7.65-7.62 (m, 4H), 4.07 (s, 6H), 1.55 (s, 36H), (s, 2H); IR
(Neat, cm-1): 1724, 1, 1700, 1609, 1475, 1368, 1278, 1108, 995, 809, 788, 764, 749; λabs/nm
(CH2Cl2): 423, 549, 588; HRMS-ESI calcd for C88H78N6O4Zn ([M+H]+): 1347.5454, found
1347.5459.
5,10-bis(4-methoxycarbonylphenyl)15,20-bis(4-diphenylaminophenyl)porphyrinato zinc(II)
o
1
(cis-Zn2TPA2E). mp ˃ 300 C; H NMR (400 MHz, CDCl3) δ = 9.16 (d, J = 2.5 Hz, 2H) 9.14
(s, 2H), 8.93 (d, J = 3.8 Hz, 2H), 8.91 ((s, 2H), 8.41 (d, J = 8.2 Hz, 4H), 8.32 (d, J = 7.7 Hz, 4H ),
8.10 (d, J = 7.6 Hz, 4H), 7.48 (d, J = 8.68 Hz, 4H), 7.44-7.43 (m, 16H), 7.18-7.14 (m, 4H), 4.08
(s, 6H); IR (Neat, cm-1): 1720, 1605, 1588, 1523, 1486, 1434, 1401, 1268, 1196, 1099, 1070,
995, 866, 717; λabs/nm (CH2Cl2): 424, 514, 552, 594; HRMS- FAB calcd for C72H50N6O4Zn
([M+]): 1126.3185, found 1126.3169.
5,10-bis(4-carbonylphenyl)15,20-bis(4-methylphenyl)porphyrinato zinc(II) (cis-Zn2T2A).
mp ˃ 300 oC; 1H NMR (400 MHz, Methanol-D4) δ = 8.86 (d, J = 4.2 Hz, 2H), 8.83 (s, 2H), , 8.82
(s, 2H), 8.79 (d, J = 4.7 Hz, 2H), 8.42 (d, J = 7.6 Hz, 4H ), 8.30 (d, J = 7.9 Hz, 4H), 8.04 (d, J =
13
74 Hz, 4H), 7.54 (d, 7.4Hz, 4H) 2.66 (s, 6H); C NMR (DMSO-D6) δ = 168.0, 150.0, 149.9,
149.4, 149.2, 147.8, 140.2, 137.1, 134.8, 134.5, 132.4, 132.2, 132.0, 131.7, 130.3, 128.0, 127.7,
121.3, 119.4, 21.5; IR (Neat, cm-1): 3397, 1683, 1605, 1274, 1205, 1180, 1070, 995, 794, 767
719; λabs/nm (THF), (ε/103 M-1 cm-1): 424 (368), 556 (16), 597 (7); λem/nm (THF): 605, 655;
HRMS- FAB calcd for C48H32N4O4Zn ([M+]): 792.1715, found 792.1717.
8

5,10-bis(4-carbonylphenyl)15,20-bis(undecyl)porphyrinato zinc(II) (cis-Zn2U2A). mp ˃ 300
1
oC; H NMR (400 MHz, DMSO-D6) δ = 13.21 (s, 2H), 8.66 (s, 2H), 9.60 (d, J = 4.6 Hz, 2H),
8.73 (d, J = 4.0 Hz, 2H), 8.65 (s, 2H ), 8.34 (d, J = 7.6 Hz, 4H), 8.24 (d, J = 7.6 Hz, 4H ) 5.00 (t,
J = 7.3 Hz, 4H), 2.44 (p, J = 7.0 Hz, 4H), 1.77 (p, J = 7.6 Hz, 4H), 1.47 (p, J = 7.3 Hz, 4H), 1.28-
1.17 (m, 24 H), 0.82 (t, J = 6.7 Hz, 6H); 13C NMR (DMSO-D6) δ = 167.5, 149.2, 149.1, 148.4,
148.3, 147.5, 134.3, 131.1, 131.0, 129.6, 127.4, 121.0, 117.4, 38.8, 31.2, 30.3, 29.7, 29.0, 28.9,
28.6, 22.0, 13.9; IR (Neat, cm-1): 3640, 1686, 1606, 1419, 1312, 1284, 1178, 1077, 1001,789,
715; λabs/nm (THF), (ε/103 M-1 cm-1): 425 (436), 559 (18), 600 (11); λem/nm (THF): 606, 652;
HRMS- FAB calcd for C56H64N4O4Zn ([M+]): 920.4219, found 920.4208.
5,10-bis(4-carboxylphenyl)15,20-bis(4-hexyl-2-thienyl)porphyrinato
zinc(II)
(cis-
Zn2TH2A). mp ˃ 300 oC; 1H NMR (400 MHz, Methanol-D4) δ = 9.04 (d, J = 4.6 Hz, 2H), 9.05
(s, 2H), 8.78-8.77 (m, 4H), 8.39 (d, J = 8.0 Hz, 4H), 8.27 (d, J = 7.9 Hz, 4H ), 7.55 (d, J = 3.2 Hz,
2H), 7.05 (d, J = 3.1 Hz, 2H), 3.02 (t, J = 7.5 Hz, 4H), 1.85 (p, J = 7.4 Hz, 4H), 1.54-1.49 (m, 4
H), 1.42-1.38 (m, 8H), 0.95 (t, J = 6.8 Hz, 6H); 13C NMR (Methanol-D4) δ = 170.1, 152.8, 152.7,
150.7, 150.8, 150.7, 149.5, 149.0, 142.7, 135.6, 134.2, 12.7, 132.4, 131.1, 128.8, 124.2, 121.5,
113.7, 33.1, 32.8, 31.1, 29.9, 23.7, 14.1; IR (Neat, cm-1): 3552, 1683, 1604, 1404, 1312, 1271,
1206, 1175, 1069, 998, 977, 822; λabs/nm (THF), (ε/103 M-1 cm-1): 429 (390), 560 (19), 601 (8);
λem/nm (THF): 618; HRMS-FAB calcd for C54H48N4O4S2Zn ([M+]): 944.2408, found 944.2400.
5,10-bis(4-carboxylphenyl)15,20-bis(3,6-di-tert-butyl-9-(thiophen-2-yl)-9H-
o
1
carbazole)porphyrinato zinc(II) (cis-Zn2TC2A). mp ˃ 300 C; H NMR (400 MHz, DMSO-
D6) δ = 13.26 (s, 2H), 9.38 (s, 2H), 9.31 (d, J = 4.6 Hz, 2H), 8.88 (d, J = 4.6 Hz, 2H), 8.79 (s,
2H), 8.40-8.38 (m, 8H), 8.33 (d, J= 8.0 Hz, 4H), 8.10 (d, J= 3.6 Hz, 2H), 7.87-7.84 (m, 6H ),
13
7.70-7.67 (m, 4H), 1.47 (s, 36H); C NMR (DMSO-D6) δ = 168.0, 151.9, 151.1, 149.5, 147.3,
146.1, 144.0, 141.5, 140.5, 140.2, 139.6, 134.8, 132.9, 130.5, 128.4, 128.0, 125.3, 124.7, 123.6,
121.3, 117.3, 111.4, 110.2, 35.1, 32.3; IR (Neat, cm-1): 1691, 1606, 1558, 1487, 1465, 1429,
1361, 1294, 1261, 1230, 1176, 1157, 1120, 999, 979, 877, 860, 794, 767, 715; λabs/nm (THF),
(ε/103 M-1 cm-1): 430 (238), 561 (12), 603 (4); λem/nm (THF): 625, 659; HRMS-ESI calcd for
C82H70N6O4S2Zn ([M+H]+): 1331.4270, found 1331.4288.
5,10-bis(4-carboxylphenyl)15,20-bis(3,6-di-tert-butyl-9-phenyl-9H-carbazole)porphyrinato
zinc(II) (cis-Zn2BC2A). mp ˃ 300 oC; 1H NMR (400 MHz, DMSO-D6) δ = 13.24 (s, 2H), 9.07
9

(s, 2H), 9.07 (d, J = 4.7 Hz, 2H), 8.87 (d, J = 4.6 Hz, 2H), 8.82 (s, 2H), 8.45 (d, J = 7.9 Hz, 4H ),
8.41-8.39 (m, 8H), 8.34 (d, J=8.0 Hz, 4H), 8.04 (d, J = 7.9Hz, 4H), 7.78 (d, J=8.6 Hz, 4H), 7.63
13
(d, J=8.3 Hz, 4H), 1.48 (s, 36H); C NMR (DMSO-D6) δ = 168.1, 150.0, 149.9, 149.5, 149.4,
147.6, 143.2, 141.6, 139.6, 139.1, 137.3, 136.1, 134.9, 132.5, 132.2, 130.4, 128.0, 125.3, 124.7,
124.3, 123.6, 120.5, 119.9, 117.2, 109.9, 35.0, 32.3; IR (Neat, cm-1): 1691, 1604, 1512, 1467,
1365, 1274, 1110, 997, 808, 794, 748; λabs/nm (THF), (ε/103 M-1 cm-1): 427 (462), 557 (20), 599
(9); λem/nm (THF): 607, 658; HRMS-ESI calcd for C86H74N6O4Zn ([M+H]+): 1319.5141, found
1319.5180.
5,10-bis(4-carbonylphenyl)15,20-bis(4-diphenylaminophenyl)porphyrinato zinc(II) (cis-
o
1
Zn2TPA2A). mp ˃ 300 C; H NMR (400 MHz, Methanol-D4) δ = 8.94 (s, 4H), 8.86 (d, J =
4.48 Hz, 2H), 8.84 (s, 2H), 8.35 (d, J = 7.6 Hz, 4H), 8.19 (d, J = 7.6 Hz, 4H ), 7.99 (d, J = 7.9 Hz,
13
4H), 7.35-7.28 (m, 20H), 7.07-7.04 (m, 4H); C NMR (DMSO-D6) δ = 168.1, 150.1, 149.9,
149.4, 149.3, 147.7, 147.2, 136.8, 135.9, 134.9, 132.6, 132.3, 132.0, 131.7, 130.4, 130.2, 128.0,
125.4, 125.0, 123.9, 121.2, 121.1, 119.5; IR (Neat, cm-1): 3564, 3374, 1690, 1584, 1403, 1330,
1282, 1196, 1074,1070, 997, 768, 753; λabs/nm (THF), (ε/103 M-1 cm-1): 430 (304), 560 (22), 602
(14); λem/nm (THF): 616; HRMS- FAB calcd for C72H46N6O4Zn ([M+]): 1098.2872, found
1098.2886.
Synthesis of Zn3TPA1A. The procedure to synthesize Zn3TPA1A is as shown in Scheme 1.
The synthetic details for condensation reaction, Zn metalation and hydrolysis are the same as
reported in table 1, 2, and 3 respectively. The free-base porphyrin 3TPA1E synthesized from a
mixed condensation is obtained in 0.93% yield. Zinc metalation of which gives 99% Zn3TPA1E.
Hydrolysis of Zn3TPA1E by KOH gives final product Zn3TPA1A in 98% yield.
1.
Scheme
of Zn3TPA1A
Synthesis
R
R
R
COOMe
BF
3.OEt2
,
N
HN
N
N
N
N
N
N
N
N
N
.2H2O
Zn(OAc)2
KOH
THF
DDQ
R
R
R
+
R
R
R
Zn
R
Zn
+
/MeOH
CH2Cl2/MeOH
N
CHO
NH
CH2Cl2
H
CHO
N
R=
COOMe
COOMe
COOH
Zn3TPA1E
Zn3TPA1A
3TPA1E
10

5-(4-methoxycarbonylphenyl)10,15,20-tris(4-diphenylaminophenyl)porphyrin (3TPA1E).
mp ˃ 300 oC; 1H NMR (400 MHz, CDCl3) δ = 9.04-9.01 (m, 6H), 8.81 (d, J = 4.6 Hz, 2H), 8.47
(d, J = 7.9 Hz, 2H), 8.33 (d, J = 7.9 Hz, 2H ), 8.11-8.08 (m, 6H), 7.49-7.46 (m, 6H), 7.44-7.40
(m, 24H), 7.17-7.13 (m, 6H), 4.13 (s, 3H), -2.66 (s, 2H); IR (Neat, cm-1): 3315, 1721, 1588,
1487, 1434, 1313, 1154, 1073, 1020, 846, 797, 693; λabs/nm (CH2Cl2): 426, 492, 516, 564,
658,748; HRMS-ESI calcd for C82H59N7O2 ([M+H]+):1174.4808, found 1174.4818.
5-(4-methoxycarbonylphenyl)10,15,20-tris(4-diphenylaminophenyl)porphyrinato zinc(II)
(Zn3TPA1E). mp ˃ 300 oC; 1H NMR (400 MHz, CDCl3) δ = 9.14-9.10 (m, 6H), 8.90 (d, J = 4.6
Hz, 2H), 8.42 (d, J = 8.0 Hz, 2H), 8.32 (d, J = 8.0 Hz, 2H ), 8.10-8.07 (m, 6H), 7.48-7.44 (m,
6H), 7.43-7.39 (m, 24H), 7.17-7.12 (m, 6H), 4.09 (s, 3H); IR (Neat, cm-1): 1721, 1587, 1484,
1402, 1312, 1176, 1176, 1110, 1026, 996, 894, 809, 794; λabs/nm (CH2Cl2): 432, 516, 554, 596;
HRMS- FAB calcd for C82H57N7O2Zn ([M+]): 1235.3865, found 1235.3850.
5-(4-carbonylphenyl)10,15,20-tris(4-diphenylaminophenyl)porphyrinato
zinc(II)
(Zn3TPA1A). mp ˃ 300 oC; 1H NMR (400 MHz, DMSO-D6) δ = 8.95-8.93 (m, 6H), 8.78 (d, J =
4.2 Hz, 2H), 8.36 (d, J = 7.6 Hz, 2H), 8.28 (d, J = 7.5 Hz, 2H ), 8.08-8.06 (m, 6H), 7.48-7.44 (m,
12H), 7.37-7.36 (m, 18H), 7.18-7.15 (m, 6H); IR (Neat, cm-1): 3535, 1694, 1587, 1523, 1404,
1204, 1175, 1071, 996, 886, 809, 718; λabs/nm (THF), (ε/103 M-1 cm-1): 435 (137), 561 (8), 605
(7); λem/nm (THF): 621; HRMS- FAB calcd for C82H55N7O2Zn ([M+]): 1221.3709, found
1221.3717.
11

NMR Spectrum of cis-2T2E
N
N
NH
HN
MeO2C
CO2Me
-2T2E
cis
HR-MS of cis-2T2E
12

NMR Spectrum of cis-2U2E
H23
C11
H23
C11
N
H
N
N
H
N
CO2Me
MeO2C
cis-2U2E
N
NH
HN
N
MeO2C
CO2Me
-2T2E
cis
HR-MS of cis-2U2E
13

NMR Spectrum of cis-2TH2E
H13
C6
H13
C6
S
S
N
N
HN
NH
H23
C11
H23
C11
N
H
CO2Me
N
MeO2C
N
-2TH2E
cis
H
N
CO2Me
MeO2C
cis-2U2E
14

HR-MS of cis-2TH2E
NMR Spectrum of cis-2TC2E
N
N
S
S
N
N
NH
HN
MeO2C
CO2Me
cis-2TC2E
15

HR-MS of cis-2TC2E
NMR Spectrum of cis-2BC2E
N
N
N
N
NH
HN
CO2Me
MeO2C
cis-2BC2E
16

HR-MS of cis-2BC2E
NMR Spectrum of cis-2TPA2E
N
N
N
N
NH
HN
MeO2C
CO2Me
cis-2TPA2E
17

HR-MS of cis-2TPA2E
NMR Spectrum of cis-Zn2T2E
N
Zn
N
N
N
MeO2C
CO2Me
-Zn2T2E
cis
18

HR-MS of cis-Zn2T2E
NMR Spectrum of cis-Zn2U2E
H23
C11
H23
C11
N
Zn
N
N
N
CO2Me
MeO2C
cis-Zn2U2E
19

HR-MS of cis-Zn2U2E
NMR Spectrum of cis-Zn2TH2E
20

H13
C6
H13
C6
S
S
N
Zn
N
N
N
CO2Me
MeO2C
-Zn2TH2E
cis
HR-MS of cis-Zn2TH2E
NMR Spectrum of cis-Zn2TC2E
21

N
N
S
S
N
Zn
N
N
N
MeO2C
CO2Me
cis-Zn2TC2E
HR-MS of cis-Zn2TC2E
22

NMR Spectrum of cis-Zn2BC2E
N
N
N
Zn
N
N
N
MeO2C
CO2Me
cis-Zn2BC2E
HR-MS of cis-Zn2BC2E
23

NMR Spectrum of cis-Zn2TPA2E
N
N
N
Zn
N
N
N
MeO2C
CO2Me
cis-Zn2TPA2E
HR-MS of cis-Zn2TPA2E
24

NMR Spectrum of cis-Zn2T2A
N
Zn
N
N
N
HOOC
COOH
-Zn2T2A
cis
HR-MS of cis-Zn2T2A
25

NMR Spectrum of cis-Zn2U2A
H23
C11
H23
C11
N
Zn
N
N
N
COOH
HOOC
cis-Zn2U2A
HR-MS of cis-Zn2U2A
26

NMR Spectrum of cis-Zn2TH2A
H13
C6
H13
C6
S
S
N
Zn
N
N
N
COOH
HOOC
-Zn2TH2A
cis
HR-MS of cis-Zn2TH2A
27

NMR Spectrum of cis-Zn2TC2A
N
N
S
S
N
Zn
N
N
N
HOOC
COOH
cis-Zn2TC2A
HR-MS of cis-Zn2TC2A
28

NMR Spectrum of cis-Zn2BC2A
N
N
N
Zn
N
N
N
COOH
HOOC
cis-Zn2BC2A
HR-MS of cis-Zn2BC2A
29