Synthesis and characterization of porphyrin sensitizers with various electron-donating substituents for highly efficient dye-sensitized solar cells

Article abstract of DOI:10.1039/b919645e

A series of porphyrin dyes with an electron-donating group (EDG) attached at a meso-position (YD1-YD8) have been designed and synthesized for use as sensitizers in dye-sensitized solar cells (DSSC). The nature of the EDG exerts a significant influence on the spectral, electrochemical and photovoltaic properties of these sensitizers. Absorption spectra of porphyrins having an amino group show broadened Soret band and red-shifted Q bands with respect to those of reference porphyrin YD0. This phenomenon is more pronounced for porphyrins YD7 and YD8 that have a π-conjugated triphenylamine at the meso-position opposite the anchoring group. Upon introduction of an EDG at the meso-position, the potential for the first oxidation alters significantly to the negative whereas that for the first reduction changes inappreciably, indicating a decreased HOMO-LUMO gap. Results of density-functional theory (DFT) calculations support the spectroelectrochemical data for a delocalization of charge between the porphyrin ring and the amino group in the first oxidative state of diarylamino-substituted porphyrins YD1-YD4, which exhibit superior photovoltaic performance among all porphyrins under investigation. With long-chain alkyl groups on the diarylamino substituent, YD2 shows the best cell performance with J_SC = 13.4 mA cm^-2, V_OC = 0.71 V, and FF = 0.69, giving an overall efficiency 6.6% of power conversion under simulated one-sun AM1.5 illumination.

Full text of DOI:10.1039/b919645e

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
Supporting Information:
Synthesis and characterization of porphyrin sensitizers with
various electron-donating substituents for highly efficient
dye-sensitized solar cells
Chou-Pou Hsieh,a Hsueh-Pei Lu,b Chien-Lan Chiu,a Cheng-Wei Lee,a Shu-Han
Chuang,a Chi-Lun Mai,a Wei-Nan Yen,a Shun-Ju Hsu,b Eric Wei-Guang Diau,*b and
Chen-Yu Yeh*a
a Department of Chemistry, National Chung Hsing University, Taichung 402, Taiwan.
E-mail: cyyeh@dragon.nchu.edu.tw.
b Department of Applied Chemistry, National Chiao Tung University, Hsinchu 300,
Taiwan. E-mail: diau@mail.nctu.edu.tw
1

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
Experiment Section
General
All reagents and solvents were obtained from commercial sources and used without
further purification unless otherwise noted. CH2Cl2 was dried over CaH2 and freshly
distilled before use. THF was dried over sodium/ benzophenone and freshly distilled
before use. Tetra-n-butylammonium hexafluorophosphate (TBAPF6) was
recrystallized twice from absolute ethanol and further dried for two days under
vacuum. Column chromatography was performed on silica gel (Merck, 70-230 Mesh
ASTM).
Spectral and Electrochemical Measurements
1H NMR spectra (Varian spectrometer) at 400 MHz, UV-visible spectra (Varian
Cary 50), UV-visible-NIR spectra (Shimadzu UV-3600), emission spectra
(a
JASCO FP-6000 spectrofluorometer), MALDI-TOF-MS and FAB-MS mass spectra
(Bruker APEX II spectrometer and a JMS-SX/SX102A Tandem Mass spectrometer,
respectively, operating in the positive ion detection mode) were recorded on the
indicated instruments. Electrochemical tests were performed with a three-electrode
potentiostat (CH Instruments, Model 750A) in THF deoxygenated on purging with
prepurified dinitrogen gas. Cyclic voltammetry was conducted with a three-electrode
cell equipped with a BAS glassy carbon (0.07 cm2) disk as the working electrode, a
platinum wire as the auxiliary electrode, and a Ag/AgCl (saturated) reference
electrode. The reference electrode is separated from the bulk solution by a double
junction filled with electrolyte solution. Potentials are reported vs. Ag/AgCl
(saturated) with reference to a ferrocene/ferrocenium (Fc/Fc+) couple at E1/2 = +0.63
vs. Ag/AgCl (saturated) at 25 °C in THF. The working electrode was polished with
0.03 μm aluminium on felt pads (Buehler) and treated ultrasonically for 1 min before
each experiment. The reproducibility of individual potential values was within ±5
mV. The spectroelectrochemical experiments were accomplished with the use of a 1
mm cuvette, a 100-mesh platinum gauze as working electrode, a platinum wire as
auxiliary electrode, and a Ag/AgCl (saturated) reference electrode.
Device Fabrication
The porphyrins were sensitized onto TiO2 nanoparticulate films to serve as working
electrodes in DSSC devices. The TiO2 nanoparticles (size ~20 nm) were
screen-printed onto the F-doped SnO2 (FTO, 30 Ω/□, Sinonar, Taiwan) glass
substrate. The TiO2 film was annealed according to a programmed procedure: (1)
heating at 80 °C for 15 min; (2) heating at 135 °C for 10 min; (3) heating at 325 °C
2

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
for 30 min; (4) heating at 375 °C for 5 min; (5) heating at 450 °C for 15 min; (6)
heating at 500 °C for 15 min. The electrode was then immersed in the
porphyrin/ethanol solution (0.2 mM, 25 °C) containing chenodeoxycholic acid
(CDCA, 0.4 mM) for dye loading onto the TiO2 film at 25 °C for 12 h. The Pt counter
electrodes were prepared on spin-coating drops of H2PtCl6 solution onto ITO glass
and heating at 380 °C for 15 min. To prevent a short circuit, the two electrodes were
assembled into a cell of sandwich type and sealed with a hot-melt film (SX1170,
Solaronix, thickness 25 μm). The electrolyte solution containing LiI (0.1 M), I2 (0.05
M), PMII (0.6 M), 4-tert-butylpyridine (0.5 M) in a mixture of acetonitrile and
valeronitrile (volume ratio 1:1) was introduced into the space between the two
electrodes, so completing the fabrication of these DSSC devices.
Photovoltaic Characterization
The current-voltage characteristics of the devices were carried out by an AM 1.5 solar
simulator (SAN-EI, XES-502S) of a class A type calibrated by a Si-based reference
cell (VLSI standards, Oriel PN 91150V). When the device is irradiated with the solar
simulator, the source meter (Keithley 2400, computer-controlled) sends a voltage (V)
to the device, and the photocurrent (I) is read at each step controlled by a computer
via a GPIB interface. The efficiency (η) of conversion of light to electricity is
obtained with these relations, η = Jsc Voc FF / Pin, in which Jsc (mA cm-2) is the current
density measured at short circuit, and Voc (V) is the voltage measured at open circuit.
Pin is the input radiation power (for one-sun illumination Pin = 100 mW cm-2) and FF
is the fill factor. The incident monochromatic photon-to-current conversion efficiency
(IPCE) spectra of the corresponding devices were obtained by a system containing a
Xe lamp (PTi A-1010, 150 W), a monochromator (Dongwoo DM150i, 1200 gr/mm
blazed at 500 nm), and a source meter (Keithley 2400, computer-controlled). A
standard Si photodiode (ThorLabs FDS1010) was used as a reference to calibrate the
power density of the light source at each wavelength. Both photocurrent densities of
the target device and the reference Si cell were measured under the same experimental
conditions (excitation beam size ~0.08 cm2) so to obtain the IPCE value of the device
from comparing the current ratio and the value of the reference cell at each
wavelength.
3

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
Synthetic Procedures.
R
Ar
Ar
Zn
Ar
R
R
N
N
N
N
N
N
N
N
+
Br
Zn
N
TIPS
TIPS
N
H
Ar
R
2a: R= hexyl
2b: R= methoxyl
2c: R= pentoxyl
1
O
OH
R
R
Ar
Ar
N
N
N
N
N
N
N
Zn
O
I
N
N
Zn
Ar
H
N
OH
Ar
R
R
YD2: R= hexyl
YD3: R= methoxyl
YD4: R= pentoxyl
Ar=
Zinc(II) 5,15-Bis(3,5-di-tert-butylphenyl)-10-(bis(4-hexylphenyl)amino)-20-
(triisoproylsilylethynyl)porphyrin (2a)
A mixture of bis(4-hexylphenyl)amine (58.5 g. 0.173 mmol), and 60% NaH (28 mg,
0.42 mmol) in dry THF (5 mL) was stirred under dinitrogen for 5 min, and then
porphyrin 1 (50 mg, 0.05 mmol), DPEphos (8 mg, 0.015 mmol) and Pd(OAc)2 (2.2
mg, 0.01 mmol) were added to the mixture. The solution was refluxed for 5 h under
dinitrogen. The solvent was removed in vacuum. The residue was purified on a
column chromatograph (silica gel) using CH2Cl2/hexane = 1/4 as the eluent.
Recrystallization from CH2Cl2/CH3OH gave 2a (39 mg, 62%). 1H NMR (CDCl3, 400
MHz) δ 9.75 (d, J = 4.8 Hz, 2H), 9.28 (d, J = 4.8 Hz, 2H), 8.95 (d, J = 4.8 Hz, 2H),
8.81 (d, J = 4.8 Hz, 2H), 8.00 (d, J = 1.6 Hz, 2H), 7.77 (d, J = 1.6 Hz, 2H), 7.21 (d, J
= 8.4 Hz, 4H), 6.96 (d, J = 8.4 Hz, 2H), 2.46 (t, J = 7.6 Hz, 4H), 1.52 (s, 36H), 1.45
13
(m, 21H), 1.24 (m, 12H), 0.82 (t, J = 7.2 Hz, 6H); C NMR (CDCl3, 100 MHz) δ
152.7, 152.5, 150.5, 150.5, 149.9, 148.6, 141.2, 134.9, 133.2, 133.1, 130.8, 130.7,
129.3, 128.9, 124.0, 123.1, 122.0, 121.0, 109.5, 100.5, 97.6, 35.2, 35.0, 31.7, 31.6,
31.4, 29.0, 22.5, 19.1, 14.0, 11.9; UV-vis (CH2Cl2): λmax/nm (ε, 103M- 1cm-1) = 428
(233), 574 (12.3), 634 (27.2); FAB-MS: m/z calcd for C83H105N5SiZn: 1264; found
4

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
1265 ([M+H]+).
Zinc(II) 5,15-Bis(3,5-di-tert-butylphenyl)-10-(bis(4-hexylphenyl)amino)-20-
(4-carboxyphenylethynyl)porphyrin (YD2)
To a solution of porphyrin 2a (25 mg, 0.02 mmol) in dry THF (5 mL) was added
o
TBAF (0.08 mL, 1M in THF). The solution was stirred at 25 C for 30 min under
dinitrogen. The mixture was quenched with H2O and then extracted with CH2Cl2. The
organic layer was dried over anhydrous Na2SO4 and the solvent was removed under
vacuum. The residue and 4-iodobenzoic acid (10 mg, 0.04 mmol) were dissolved in
dry THF (5 mL) and NEt3 (1 mL) and degassed with dinitrogen for 10 min, and then
Pd2(dba)3 (4.4 mg, 0.005 mmol) and AsPh3 (12 mg, 0.04 mmol) were added to the
mixture. The solution was refluxed for 4.5 h under dinitrogen. The solvent was
removed under vacuum. The residue was purified on a column chromatograph (silica
gel) using CH2Cl2/CH3OH = 20/1 as the eluent. Recrystallization from
1
CH2Cl2/CH3OH gave YD2 (20.6 mg, 85%). H NMR (CDCl3/pyridine-d5, 400 MHz)
δ 9.79 (d, J = 4.8 Hz, 2H), 9.29 (d, J = 4.8 Hz, 2H), 9.00 (d, J = 4.8 Hz, 2H), 8.83 (d,
J = 4.8 Hz, 2H), 8.27 (d, J = 8.4 Hz, 2H), 8.11 (d, J = 8.4 Hz, 2H), 8.03 (d, J = 1.6 Hz,
4H), 7.79 (d, J = 1.6 Hz, 2H), 7.22 (d, J = 9.2 Hz, 4H), 6.98 (d, J = 9.2 Hz, 4H), 2.47
13
(t, J = 7.6 Hz, 4H), 1.50 (s, 36H), 1.26 (m, 16H), 0.84 (t, J = 7.2 Hz, 6H); C NMR
(CDCl3, 100 MHz) δ 168.9, 152.2, 150.6, 150.3, 149.9, 148.4, 141.7, 134.6, 132.9,
131.1, 130.1, 129.7, 128.8, 123.8, 123.3, 123.1, 122.8, 121.9, 120.6, 98.5, 96.7, 95.3,
35.2, 35.0, 31.7, 31.4, 29.0, 22.5, 14.0; UV-vis (ethanol): λmax/nm (ε, 103M- 1cm-1) =
444 (217), 589 (10.8), 648 (33.7); FAB-MS: m/z calcd for C81H89N5O2Zn: 1228;
found 1228 ([M]+).
Zinc(II) 5,15-Bis(3,5-di-tert-butylphenyl)-10-(bis(4-methoxyphenyl)amino)-20-
(triisopropylsilylethynyl)porphyrin (2b)
A mixture of bis(4-methoxyphenyl)amine (40 mg, 0.175 mmol), and 60% NaH (28
mg, 0.42 mmol) in dry THF (10 mL) was stirred under dinitrogen for 5 min, and then
porphyrin 1 (50 mg, 0.05 mmol), DPEphos (8 mg, 0.015 mmol) and Pd(OAc)2 (2.2
mg, 0.01 mmol) were added to the mixture. The solution was refluxed for 5 h under
dinitrogen. The solvent was removed in vacuum. The residue was purified on a
column chromatograph (silica gel) using CH2Cl2/hexane = 1/3 as the eluent.
Recrystallization from CH2Cl2/CH3OH gave 2b (24 mg, 42 %). 1H NMR
(CDCl3/pyridine-d5, 400 MHz) δ 9.66 (d, J = 4.8 Hz, 2H), 9.15 (d, J = 4.8 Hz, 2H),
5

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
8.84 (d, J = 4.8 Hz, 2H), 8.70 (d, J = 4.8 Hz, 2H), 7.94 (d, J = 1.6 Hz, 4H), 7.73 (d, J
= 1.6 Hz, 2H), 7.16 (d, J = 9.2 Hz, 4H), 6.66 (d, J = 9.2 Hz, 4H), 3.68 (s, 6H), 1.50 (s,
36H), 1.45-1.43 (m, 21H); 13C NMR (CDCl3, 100 MHz) δ 153.2, 152.7, 152.1, 150.3,
149.6, 148.3, 147.1, 141.8, 132.8, 130.4, 130.2, 129.4, 123.1, 122.8, 120.7, 114.3,
110.5, 99.4, 96.4, 55.4, 34.9, 31.7, 19.1, 11.9; UV-vis (CH2Cl2): λmax/nm (ε, 103M-
1cm-1) = 435 (189), 590 (6.9), 652 (17.2); FAB-MS: m/z calcd for C73H85N5O2SiZn:
1156; found 1157 ([M+H]+).
Zinc(II) 5,15-Bis(3,5-di-tert-butylphenyl)-10-(bis(4-methoxyphenyl)amino)-20-
(4-carboxylphenylethynyl)porphyrin (YD3)
To a solution of porphyrin 2b (24.0 mg, 0.02 mmol) in dry THF (5 mL) was added
o
TBAF (0.08 mL, 1M in THF). The solution was stirred at 25 C for 30 min under
dinitrogen. The mixture was quenched with H2O and then extracted with CH2Cl2. The
organic layer was dried over anhydrous Na2SO4 and the solvent was removed under
vacuum. The residue and 4-iodobenzoic acid (10 mg, 0.04 mmol) were dissolved in
dry THF (5 mL) and NEt3 (1 mL) and degassed with dinitrogen for 10 min, and then
Pd2(dba)3 (4.4 mg, 0.005 mmol) and AsPh3 (12 mg, 0.04 mmol) were added to the
mixture. The solution was refluxed for 4.5 h under dinitrogen. The solvent was
removedunder vacuum. The residue was purified on a column chromatograph (silica
gel) using CH2Cl2/CH3OH = 30/1 as the eluent. Recrystallization from
CH2Cl2/CH3OH gave YD3 ( 13.9 mg, 60 %). 1H NMR (CDCl3/pyridine-d5, 400 MHz)
δ 9.71 (d, J = 4.8 Hz, 2H), 9.17 (d, J = 4.8 Hz, 2H), 8.89 (d, J = 4.8 Hz, 2H), 8.72 (d,
J = 4.8 Hz, 2H), 8.30 (d, J = 8.0 Hz, 2H), 8.07 (d, J = 8.0 Hz, 2H), 7.96 (d, J = 1.6 Hz,
4H), 7.75 (d, J = 1.6 Hz, 2H), 7.17 (d, J = 9.2 Hz, 4H), 6.68 (d, J = 9.2 Hz, 4H), 3.68
(s, 6H), 1.51 (s, 36H); 13C NMR (CDCl3, 100 MHz) δ 168.9, 153.2, 152.3, 152.2,
150.3, 149.8, 148.5, 147.2, 141.7, 135.8, 131.1, 130.8, 130.4, 130.1, 129.7, 128.8,
124.3, 123.2, 120.7, 98.4, 96.6, 95.3, 55.4, 34.9, 31.7; UV-vis (ethanol): λmax/nm (ε,
103M- 1cm-1) = 440 (141), 592 (5.9), 664 (16.9); FAB-MS: m/z calcd for
C71H69N5O4Zn: 1120; found 1121 ([M+H] +).
Zinc(II) 5,15-Bis(3,5-di-tert-butylphenyl)-10-(bis(4-pentoxyphenyl)amino)-20-
(triisopropylsilylethynyl)porphyrin (2c)
A mixture of bis(4-pentoxylphenyl)amine (178 mg, 0.52 mmol), and 60% NaH (84
6

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
mg, 2.1 mmol) in dry THF (20 mL) was stirred under dinitrogen for 5 min, and then
porphyrin 1 (150 mg, 0.15 mmol), DPEphos (24.0 mg, 0.04 mmol) and Pd(OAc)2 (6.6
mg, 0.03 mmol) were added to the mixture. The solution was refluxed for 5 h under
dinitrogen. The solvent was removed in vacuum. The residue was purified on a
column chromatograph (silica gel) using CH2Cl2/hexane = 1/3 as the eluent.
Recrystallization from CH2Cl2/CH3OH gave 2c (75.4 mg, 40%). 1H NMR
(CDCl3/pyridine-d5, 400 MHz) δ 9.66 (d, J = 4.8 Hz, 2H), 9.15 (d, J = 4.8 Hz, 2H),
8.84 (d, J = 4.8 Hz, 2H), 8.69 (d, J = 4.8 Hz, 2H), 7.93 (d, J = 1.6 Hz, 4H), 7.72 (d, J
= 1.6 Hz, 2H), 7.13 (d, J = 9.2 Hz, 4H), 6.65 (d, J = 9.2 Hz, 4H), 3.81 (t, J = 6.4 Hz,
4H), 1.68 (m, 4H), 1.49 (s, 36H), 1.45-1.43 (m, 21H), 1.32-1.27 (m, 8H), 0.85 (t, J =
7.2 Hz, 6H); 13C NMR (CDCl3, 100 MHz) δ 152.9, 152.8, 152.6, 150.4, 149.8, 148.7,
147.0, 141.3, 133.1, 130.7, 129.4, 124.6, 123.2, 123.1, 121.0, 115.2, 109.6, 100.3,
97.5, 68.3, 50.1, 35.0, 31.7, 29.0, 28.2, 22.4, 19.1, 18.8, 18.5, 13.9, 12.0; UV-vis
(CH2Cl2): λmax/nm (ε, 103M- 1cm-1) = 434 (191), 589 (7.1), 650 (17.9); FAB-MS: m/z
calcd for C81H101N5O2SiZn: 1268; found 1269 ([M+H]+).
Zinc(II) 5,15-Bis(3,5-di-tert-butylphenyl)-10-(bis(4-pentoxyphenyl)amino)-20-
(4-carboxylphenylethynyl)porphyrin (YD4)
To a solution of porphyrin 2c (50 mg, 0.04 mmol) in dry THF (5 mL) was added
o
TBAF (0.16 mL, 1M in THF). The solution was stirred at 25 C for 30 min under
dinitrogen. The mixture was quenched with H2O and then extracted with CH2Cl2. The
organic layer was dried over anhydrous Na2SO4 and the solvent was removed under
vacuum. The residue and 4-iodobenzoic acid (20 mg, 0.08 mmol) were dissolved in
dry THF (5 mL) and NEt3 (1 mL) and degassed with dinitrogen for 10 min, and then
Pd2(dba)3 (9 mg, 0.01 mmol) and AsPh3 (30 mg, 0.09 mmol) were added to the
mixture. The solution was refluxed for 4.5 h under dinitrogen. The solvent was
removed under vacuum. The residue was purified on a column chromatograph (silica
gel) using CH2Cl2/CH3OH = 60/1 as the eluent. Recrystallization from
1
CH2Cl2/methanol gave YD4 ( 31.5 mg, 65 %). H NMR (CDCl3/pyridine-d5, 400
MHz) δ 9.70 (d, J = 4.8 Hz, 2H), 9.16 (d, J = 4.8 Hz, 2H), 8.88 (d, J = 4.8 Hz, 2H),
8.70 (d, J = 4.4 Hz, 2H), 8.30 (d, J = 8.4 Hz, 2H), 8.07 (d, J = 8.4 Hz, 2H), 7.96 (d, J
= 1.6 Hz, 4H), 7.74 (d, J = 1.6 Hz, 2H), 7.15 (d, J = 9.2 Hz, 4H), 6.67 (d, J = 9.2 Hz,
4H), 3.82 (t, J = 6.4 Hz, 4H), 1.68 (m, 4H), 1.50 (s, 36H), 1.37-1.29 (m, 8H), 0.86 (t,
13
J = 7.2 Hz, 6H); C NMR (CDCl3, 100 MHz) δ 153.0, 152.7, 152.4, 150.4, 150.0,
148.8, 147.0, 141.1, 133.4, 133.2, 131.4, 130.9, 130.4, 129.9, 129.6, 128.2, 125.2,
7

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
123.6, 123.3, 121.1, 115.2, 114.8, 99.0, 96.6, 95.4, 68.3, 35.1, 31.8, 29.0, 28.2, 22.4,
13.9; UV-vis (ethanol): λmax/nm (ε, 103M- 1cm-1) = 438 (143), 591 (5.4), 653 (17.6);
FAB-MS: m/z calcd for C79H85N5O4Zn: 1232; found 1232 ([M]+).
Preparation of arylamine 51
N-tert-Butoxycarbonyl-N,N-bis[4-(di-tert-butylphenylamino)phenyl]amine (4)
Dibrominated arylamine 3 (0.45 g, 1.05 mmol), bis(4-tert-butylphenyl)amine (0.89 g,
3.16 mmol), sodium tert-butoxide (0.39 g, 4.05 mmol), Pd(OAc)2 (15.95 mg,
0.0725 mmol) and 1,1′-bis-(diphenylphosphanyl)ferrocene (DPPF) (76.5 mg, 0.139
mmol), were dissolved in toluene (15 mL) in a Schlenk flask under argon. The
reaction mixture was heated to reflux for 96 h. The mixture was wased with water and
then dried over MgSO4. The solvent was removed under vacuum. The residue was
purified on a column chromatograph (silica gel) using CH2Cl2/hexane = 2/1 as the
1
eluent afforded pure 4 (0.52 g, 65%). H NMR (CDCl3, 400 MHz) δ 7.25 (m, 8H),
13
7.09 (d, J = 8.8 Hz, 4H), 7.04-7.00 (m, 12H), 1.48 (s, 9H), 1.31 (s, 36H); C NMR
(CDCl3, 100 MHz) δ 154.3, 145.6, 145.5, 145.1, 137.0, 127.4, 126.0, 123.8, 123.3,
80.8, 34.2, 29.4, 28.3; FAB-MS: m/z calcd for C57H69N3O2: 827 ; found 827 ([M]+).
N,N-Bis[4-(di-tert-butylphenylamino)phenyl]amine (5)
Compound 4 (0.5 g, 0.6 mmol) was dissolved in trifluoracetic acid (15.3 mL) and the
reaction mixture was stirred at room temperature for 10 min. After evaporation of
TFA, toluene was added to the residue, then the mixture washed with saturated
aqueous solution of NaOH and dried over MgSO4. Evaporation of solvent and
1
recrystallization from hexane/toluene affored pure 5 (365 mg, 83%). H NMR
(DMSO-d6, 400 MHz) δ 7.78 (br, 1H), 7.14 (br, 8H), 6.97-6.94 (m, 4H), 6.89-6.84 (m,
12H), 1.22 (s, 36H); 13C NMR (CDCl3, 100 MHz) δ 145.4, 144.3, 141.9, 138.6, 126.2,
8

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
125.6, 122.3, 118.5, 34.0, 31.2; FAB-MS: m/z calcd for C52H61N3: 727; found 728
([M+H]+).
Ar
Ar
Ar
N
Ar
Ar
N
N
N
N
N
N
N
N
5
+
N
Br
Zn
Zn
TIPS
TIPS
Ar
Ar
N
Ar
6
1
O
OH
Ar
Ar
Ar
Ar
N
Ar
Ar
N
Ar
Zn
Ar
Ar
N
N
N
N
N
N
N
I
N
N
H
Zn
Ar
COOH
N
N
N
Ar
Ar
YD5
Ar=
Zinc(II) 5,15-Bis(3,5-di-tert-butylphenyl)-10-(N,N-bis(4-(di-tert-butylphenyl-
amino)phenyl)amino)-20-(triisopropylsilylethynyl)porphyrin (6)
A mixture of N,N-bis[4-(di-tert-butylphenylamino)phenyl]amine (126 mg, 0.17
mmol), and 60% NaH (28 mg, 0.42 mmol) in dry THF (10 mL) was stirred under
dinitrogen for 5 min, and then porphyrin 1 (50 mg, 0.05 mmol), DPEphos (8 mg,
0.015 mmol) and Pd(OAc)2 (2.2 mg, 0.01 mmol) were added to the mixture. The
solution was refluxed for 5 h under dinitrogen. The solvent was removed in vacuum.
The residue was purified on a column chromatograph (silica gel) using
CH2Cl2/hexane = 1/3 as the eluent. Recrystallization from CH2Cl2/CH3OH gave 6
(36.1 mg, 45%). 1H NMR (CDCl3, 400 MHz) δ 9.75 (d, J = 4.8 Hz, 2H), 9.35 (d, J =
4.8 Hz, 2H), 8.97 (d, J = 4.8 Hz, 2H), 8.87 (d, J = 4.8 Hz, 2H), 8.04 (d, J = 1.6 Hz,
4H), 7.81 (d, J = 1.6 Hz, 2H), 7.21 (d, J = 8.8 Hz, 4H), 7.15 (d, J = 6.8 Hz, 2H), 6.95
(d, J = 6.8 Hz, 2H), 6.90 (d, J = 8.8 Hz, 4H), 1.53 (s, 36H), 1.50-1.43 (m, 21H), 1.26
(s, 36H); 13C NMR (CDCl3, 100 MHz) δ 152.7, 152.4, 150.4, 149.9, 148.7, 148.0,
145.3, 144.7, 141.2, 140.8, 133.2, 133.1, 130.9, 130.7, 129.4, 125.7, 125.2, 123.2,
122.9, 121.0, 109.4, 100.6, 97.7, 35.0, 34.1, 31.7, 31.3, 29.7, 19.1, 11.9; UV-vis
9

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
(CH2Cl2): λmax/nm (ε, 103M- 1cm-1) = 432 (339), 646 (31.5); FAB-MS: m/z calcd for
C111H131N7SiZn: 1655; found 1655 ([M]+).
Zinc(II) 5,15-Bis(3,5-di-tert-butylphenyl)-10-(N,N-bis(4-(di-tert-butylphenyl-
amino)phenyl)amino)-20-(4-carboxylphenylethynyl)porphyrin (YD5)
To a solution of porphyrin 6 (33 mg, 0.02 mmol) in dry THF (5 mL) was added TBAF
(0.08 mL, 1M in THF). The solution was stirred at 25 oC for 30 min under dinitrogen.
The mixture was quenched with H2O and then extracted with CH2Cl2. The organic
layer was dried over anhydrous Na2SO4 and the solvent was removed under vacuum.
The residue and 4-iodobenzoic acid (10 mg, 0.04 mmol) were dissolved in dry THF
(10 mL) and NEt3 (2 mL) and degassed with dinitrogen for 10 min, and then
Pd2(dba)3 (4.4 mg, 0.005 mmol) and AsPh3 (15 mg, 0.045 mmol) were added to the
mixture. The solution was refluxed for 4.5 h under dinitrogen. The solvent was
removed under vacuum. The residue was purified on a column chromatograph (silica
gel) using CH2Cl2/CH3OH = 50/1 as the eluent. Recrystallization from
CH2Cl2/CH3OH gave YD5 ( 21.5 mg, 67 %). 1H NMR (CDCl3, 400 MHz) δ 9.77 (d, J
= 4.8 Hz, 2H), 9.36 (d, J = 4.8 Hz,2H), 9.02 (d, J = 4.4 Hz, 2H), 8.89 (d, J = 4.4 Hz,
2H), 8.24 (d, J = 7.6 Hz, 2H), 8.10 (d, J = 7.6 Hz, 2H), 8.08 (d, J = 1.6 Hz, 4H), 7.83
(d, J = 2.0 Hz, 2H), 7.23-7.15 (m, 12H), 6.98-6.91 (m, 12H), 1.58 (s, 36H), 1.26 (s,
36H); 13C NMR (CDCl3, 100 MHz) δ 152.5, 152.4, 150.4, 151.0, 148.8, 148.1, 145.3,
144.7, 141.1, 140.9, 133.4, 133.3, 131.4, 130.4, 129.7, 125.7, 125.2, 123.6, 123.0,
122.9, 121.0, 99.2, 96.5, 95.5, 35.1, 34.1, 31.8, 31.4; UV-vis (ethanol): λmax/nm (ε,
103M- 1cm-1) = 441 (307), 659 (27.2); FAB-MS: m/z calcd for C109H115N7O2Zn: 1619;
found 1621 ([M+2H]+).
10

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
O
Ar
Ar
O
N
N
N
N
N
N
N
N
O
N
B
Zn
Si
Zn
Si
N
+
I
O
O
Ar
Ar
O
7
9
8
CO2H
Ar
Ar
O
O
O
N
N
N
N
N
N
N
I
H
CO2H
Zn
Zn
N
N
N
Ar
Ar
O
YD6
10
Ar =
Zinc(II) 5-(triisopropylsilylethynyl)-10,20-bis(3,5-di-tert-butylphenyl)-15-(N,N-
bis(4-methoxyphenyl)aminophenyl)porphyrin (9)
A mixture of compound 7 (8 mg, 0.02 mmol) and porphyrin 8 (13 mg, 0.01 mmol) in
dry DMF (6 mL) degassed with nitrogen for 10 mins, and then K3PO4 (10 mg, 0.05
mmol) and Pd(PPh3)4 (4 mg, 3 μmol) were added. The reaction mixture was stirred
for 3 h at temperature 90 ℃ and then extrated with CH2Cl2. Before the solvent was
evaporated to dryness in vacuum, the organic layer was washed with Na2SO4. The
product was purified by column chromatography on silica gel using CH2Cl2:Hexane
(1:2) as the eluent. Solvent was removed under reduced pressure and the residue was
then recrystallized from CH2Cl2/CH3OH to give a pure dark blue solid (10 mg, 66
％).1H NMR (400 MHz, CDCl3) δH = 9.80 (d, J = 4.8 Hz, 2H), 9.03 (d, J = 4.8 Hz,
4H), 8.92 (d, J = 4.8 Hz, 2H), 8.06 (d, J = 4.8 Hz, 4H), 7.96 (d, J = 8.4 Hz, 2H), 7.81
(s, 2H), 7.34 (d, J = 9.2 Hz, 4H), 7.27 (d, J = 8.4 Hz, 2H), 6.95 (d, J = 9.2 Hz, 4H),
3.84 (s, 6H), 1.54 (s, 36H), 1.44-1.42 (m, 21H) ; 13C NMR (75 MHz, CDCl3) δ 156.1,
152.7, 150.7, 150.1, 148.6, 141.0, 135.0, 133.2, 132.2, 131.9, 130.8, 129.5, 127.0,
123.2, 120.9, 118.1, 114.9, 55.53, 35.0, 31.8, 30.9, 29.7, 19.1, 11.9; UV/Vis :
(CH2Cl2): λmax/nm (ε, 103M- 1cm-1) = 431 (33.8), 563 (19.5), 609 (21,4); FAB-MS:
m/z calcd for C79H89N5O2SiZn: 1232; found 1233 ([M+H]+).
11

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
Zinc(II) 5-(4-Carboxyphenylethynyl)-10,20-bis(3,5-di-tert-butylphenyl)-15-(N,N-
bis(4-methoxyphenyl)aminophenyl)porphyrin (YD6)
To a solution of porphyrin 9 (17 mg, 0.02 mmol) in dry THF (5 mL) was added
o
TBAF (0.08 mL, 1M in THF). The solution was stirred at 25 C for 30 min under
dinitrogen. The mixture was quenched with H2O and then extracted with CH2Cl2. The
organic layer was dried over anhydrous Na2SO4 and the solvent was removed under
vacuum. The residue and 4-iodobenzoic acid (6.0 mg, 0.02 mmol) were dissolved in
dry THF (10 mL) and NEt3 (5 mL) and degassed with dinitrogen for 10 min, and then
Pd2(dba)3 (2.0 mg, 2 μmol) and AsPh3 (1.0 mg, 3 μmol) were added to the mixture.
The solution was refluxed for 4.5 h under dinitrogen. The solvent was removed under
vacuum. The residue was purified on a column chromatograph (silica gel) using
CH2Cl2/CH3OH = 9/1 as the eluent. Recrystallization from CH2Cl2/methanol gave
1
YD6 (12 mg, 63 %). H NMR (400 MHz, CDCl3/pyridine-d5) δH = 9.27 (d, J = 4.8
Hz, 2H), 8.97 (d, J = 4.8 Hz, 2H), 8.94 (d, J = 4.8 Hz, 2H), 8.84 (d, J = 4.8 Hz, 2H),
8.30 (d, J = 8.4 Hz, 2H), 8.09 (d, J = 8.4 Hz, 2H), 8.04 (s, 4H), 7.96 (d, J = 8.4 Hz,
2H), 7.79 (s, 2H), 7.33 (d, J = 9.2 Hz, 4H), 7.26 (d, J = 8.4 Hz, 2H), 6.95 (d, J = 9.2
Hz, 4H), 3.84 (s, 6H), 1.54 (s, 36H); 13C NMR (75 MHz, CDCl3/pyridine-d5) δ 155.94,
150.75, 149.96, 148.35, 147.97, 142.01, 141.17, 135.16, 133.06, 131.63, 131.09,
129.95, 126.85, 123.43, 123.28, 123.10, 122.77, 120.58, 118.20, 114.83, 55.52, 35.01,
31.75, 29.68; UV/Vis (ethanol): λmax/nm (ε, 103M- 1cm-1) = 443 (216), 579 (8.0), 628
(20.8); FAB-MS: m/z calcd for C77H73N5O4Zn: 1196; found 1197 ([M+H]+).
HO
O
O
O
N
I
I
N
N
N
N
N
N
N
N
TIPS
TIPS
H
H
Zn
Zn
10
O
N
N
N
Zn
N
N
COOH
O
YD8
12

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
Zinc(II) 5,15-Bis(3,5-di-tert-butylphenyl)-10-(N,N-bis(3,5-di-tert-butyl-4-
methoxyphenyl)aminophenylethynyl)-20-(4-carboxylphenylethynyl)porphyrin
(YD8)
To a solution of porphyrin 10 (100 mg, 0.125 mmol) in dry THF (5 mL) was added
o
TBAF (0.24 mL, 1M in THF). The solution was stirred at 25 C for 30 min under
dinitrogen. The mixture was quenched with H2O and then extracted with CH2Cl2. The
organic layer was dried over anhydrous Na2SO4 and the solvent was removed under
vacuum. The residue , 4-iodobenzoic acid (37 mg, 0.15 mmol) and
N,N-bis(3,5-di-tert-butyl-4-methoxyphenyl)-N-(4-iodophenyl)amine (98 mg, 0.15
mmol) were dissolved in dry THF (60 mL) and NEt3 (12.5 mL) and degassed with
dinitrogen for 10 min, and then Pd2(dba)3 (34 mg, 0.038 mmol) and AsPh3 (95 mg,
0.03 mmol) were added to the mixture. The solution was refluxed for 4.5 h under
dinitrogen. The solvent was removed under vacuum. The residue was purified by
column chromatography on silica gel using CH2Cl2/CH3OH = 9.5/1 as the eluent.
1
Recrystallization from CH2Cl2/CH3OH gave YD8 ( 21.5 mg, 70 %)。H NMR (CDCl3,
400 MHz) δ 9.71 (d, J = 4.8 Hz, 2H), 9.69 (d, J = 4.8 Hz, 2H), 8.89 (d, J = 4.8 Hz,
4H), 8.87 (d, J = 4.8 Hz, 2H), 8.30 (d, J = 8.4 Hz, 2H), 8.07 (d, J = 8.4 Hz, 2H), 8.01
(d, J = 1.6 Hz, 4H), 7.82 (d, J = 8.8 Hz, 2H), 7.78 (d, J = 1.6 Hz, 2H), 7.15 (d, J = 8.8
Hz, 2H), 7.06 (s, 4H), 1.53 (s, 36H), 1.38 (s, 36H); 13C NMR (CDCl3, 100 MHz) δ
155.7, 152.0, 151.6, 150.3, 150.2, 148.5, 144.3, 141.7, 141.5, 132.9, 132.5, 132.2,
131.1, 130.2, 130.1, 129.9, 123.5, 120.7, 120.5, 115.2, 102.4, 101.8, 99.3, 97.5, 96.4,
95.63, 92.5, 64.2, 35.9, 35.0, 32.1, 31.7; UV-vis (ethanol): λmax/nm (ε, 103M- 1cm-1) =
457 (136), 671 (49.9); FAB-MS: m/z calcd for C95H105N5O4Zn: 1446; found 1448
([M+2H]+).
References
1. Y. Hirao, H. Ino, A. Ito and K. Tanaka, J. Phys. Chem. A, 2006, 110, 4866-4872.
13

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
14

Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2009
Fig. S1 Schematic diagram for the spectroelectrochemical cell.
15