Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of...

22
S1 Supporting Information A meso-meso directly linked porphyrin dimer-based double D-π-A sensitizer for efficient dye-sensitized solar cells Tao Zhang, Xing Qian, Peng-Fei Zhang, Yi-Zhou Zhu* and Jian-Yu Zheng* State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China E-mail: [email protected]; [email protected]. Table of Contents General......................................................................................................................S2 Fabrication and characterization of DSSCs..........................................................S2 Optical Spectroscopy ................................................................................................S2 Dye-loading examination.........................................................................................S3 Synthetic procedure..................................................................................................S3 Fluorescence spectra of JY06 and JY07 in THF ....................................................S8 Frontier orbitals of JY06 and JY07 (HOMO and LUMO)...................................S8 FTIR spectra of JY06 and JY07 powders and stained TiO 2 films........................S8 Photovoltaic performance for DSSCs based on JY07............................................S8 Photostability study...................................................................................................S9 Electrochemical impedance spectroscopy (EIS) ....................................................S9 References.................................................................................................................S10 1 H NMR and 13 C NMR spectra.…..........................................................................S11 HR-MS spectra.…....................................................................................................S19 Electronic Supplementary Material (ESI) for ChemComm. This journal is © The Royal Society of Chemistry 2015

Transcript of Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of...

Page 1: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S1

Supporting Information

A meso-meso directly linked porphyrin dimer-based double

D-π-A sensitizer for efficient dye-sensitized solar cells

Tao Zhang Xing Qian Peng-Fei Zhang Yi-Zhou Zhu and Jian-Yu Zheng

State Key Laboratory and Institute of Elemento-Organic Chemistry Collaborative Innovation

Center of Chemical Science and Engineering (Tianjin) Nankai University Tianjin 300071 China

E-mail zhuyizhounankaieducn jyzhengnankaieducn

Table of Contents

GeneralS2

Fabrication and characterization of DSSCsS2

Optical SpectroscopyS2

Dye-loading examinationS3

Synthetic procedureS3

Fluorescence spectra of JY06 and JY07 in THFS8

Frontier orbitals of JY06 and JY07 (HOMO and LUMO)S8

FTIR spectra of JY06 and JY07 powders and stained TiO2 filmsS8

Photovoltaic performance for DSSCs based on JY07S8

Photostability studyS9

Electrochemical impedance spectroscopy (EIS) S9

ReferencesS10

1H NMR and 13C NMR spectrahellipS11

HR-MS spectrahellipS19

Electronic Supplementary Material (ESI) for ChemCommThis journal is copy The Royal Society of Chemistry 2015

S2

General All solvents were purified according to standard methods Other chemicals (AR) obtained from

commercial sources were used without further purification NMR solvents were used as received 1H NMR and 13C NMR spectra were recorded on Bruker 400 MHz spectrometer using TMS as the

internal standard UV-vis spectra were obtained on a Varian Cary 300 Conc UV-visible

spectrophotometer HR-MS data was measured on a Varian 70T FTMS IR spectra were recorded

on a Bio-rad FTS6000 spectrometer Elementary analyses were performed using a Vario EL CUBE

Analyzer Cyclic voltammetry experiments and electrochemical impedance spectroscopy were

recorded on a Zennium electrochemical workstation (Zahner Germany) Electrochemical

impedance spectroscopy was recorded in the dark under -060 V bias The frequencies explored

ranged from 100 mHz to 100 kHz Cyclic voltammetry experiments were carried out using a

conventional three-electrode system employing glassy carbon electrode as the working electrode

AgAg+ electrode as the reference electrode and Pt wire as the counter electrode The redox

potentials were measured in THF using 01 M n-Bu4NPF6 as supporting electrolyte with a scan

rate of 100 mV S-1 Dipyrromethane1 4-Octyloxyiodobenzene2

NN-bis(4-octyloxyphenyl)aniline2 4-(bis(4-(octyloxy)phenyl)amino)benzaldehyde3 were

synthesized according to literature methods

Fabrication and characterization of DSSCs The DSSCs were fabricated according to a previous literature procedure4 A TiO2 film (~10 microm)

for the transparent nanocrystalline layer was prepared by doctor-blade method coating a

commercial 20 nm TiO2 sol (China National Academy of Nanotechnology amp Engineering) onto

the treated FTO conductive glass (Nippon Sheet Glass Japan fluorine-doped SnO2 over layer

sheet resistance of 15 Ωsq treated with TiCl4 (005 M) solution) The scattering layer (~4 microm)

was applied over the transparent layer by doctor-blade method then gradually heated to 500degC

and sintered for 60 min The resulting TiO2 electrodes were treated by TiCl4 and sintered again at

500degC for 60 min The Pt electrode was obtained by thermal deposition of a platinum layer onto

the surface of FTO at 450degC for 30 min The TiO2 thin film was dipped into the 03 mM dye

solution in THF for at least 12 h The electrolyte was composed of 03 M DMPII 01 M LiI 005

M I2 and 05 M 4-tert-butylpyridine in acetonitrile The DSSCs were illuminated by a solar

simulator (Orielreg Sol2A Newport Corporation) under 100 mWcm2 irradiation which was

calibrated by a standard silicon solar cell The photocurrent intensity-voltage (J-V) characteristic

curves of the DSSC under simulated sunlight were recorded using an IM6ex electrochemical

workstation (Zahner Germany) The measurement of the incident photon-to-current conversion

efficiency (IPCE) was performed by using a commercial setup (QTest Station 2000 IPCE

Measurement System CROWNTECH USA)

Optical Spectroscopy UVVis absorption spectra of the porphyrins in THF and adsorbed onto TiO2 electrodes were

recorded on a Varian Cary 300 Conc UV-visible spectrophotometer For the absorption spectra of

the thin films on TiO2 TiO2 films (area 1times1 cm2) were prepared with thicknesses of about 1μm to

obtain comparable shapes and peak positions The films were immersed in 03 mM solutions of

the porphyrins in THF for 5 minutes and the films were rinsed with THF dried and the

absorbance was measured (Transmittance UV spectra) Steady-state fluorescence spectra were

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acquired on a Varian Cary Eclipse fluorescence spectrophotometer

Dye-loading examination To determine the dye-loading amount of JY06 and JY07 on TiO2 films the dye adsorbed on TiO2

(04 cm times 04 cm) was desorbed in 02 M KOH (aq) in THF (28 vv) The calibration curves for

JY06 and JY07 in 02 M KOH (aq) in THF (28 vv) were derived to obtain the absorption

coefficients The amounts of dye-loading on TiO2 films were obtained from the measured

absorbances of the Soret bands in the spectra and the calibrated absorption coefficients at the same

spectral position according to Beersrsquo law

In fact more than 12 h exposure to commonly used 01 M aqueous solution of KOH in THF (28

vv) was unable to completely desorb the dye JY07 from TiO2 Instead a 02 M aqueous solution

of KOH in THF (28 vv) was used to desorb the dye from TiO2 The requirement of a higher

concentration of the base to desorb the dye from TiO2 provides further evidence of a stronger

adhesion of the double D-π-A dye than the porphyrin dye that possessed a single anchoring group

Synthetic procedure

Reagents (i) TFA DDQ (ii) NBS (iii) a) Phenylboronic acid Pd(PPh3)4 Cs2CO3 b)

Zn(OAc)22H2O (iv) PIFA (v) KOH EtOHH2OTHF

N

NH N

HN

NR R

Br Br

COOCH3

N

N N

N

NR R

COOCH3

ZnN

N N

N

NR R

COOH

ZnN

NH N

HN

NR R

COOCH31 5 6 JY06

(i) (ii) (iii)

R=

OC8H17

Reagents (i) NBS (ii) a) Phenylboronic acid Pd(PPh3)4 Cs2CO3 b) Zn(OAc)22H2O (iii) KOH

EtOHH2OTHF

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Scheme S1 Syntheses of JY06 and JY07

Synthesis of compound 1 To a degassed solution of dipyrromethane (731 mg 5 mmol)

4-(bis(4-(octyloxy)phenyl)amino)benzaldehyde (132 g 25 mmol) and methyl 4-formylbenzoate

(4105 mg 25 mmol) in CH2Cl2 (500 mL) was added CF3COOH (022 mL 3 mmol) The mixture

was stirred in the dark for 10 h and then DDQ (10 g 45mmol) was added After another 1 h

Et3N (50 mL) was added and the solvent was removed under reduced pressure Purification by

silica gel column chromatography (CH2Cl2PE = 31) and recrystallization from CH2Cl2MeOH

afforded compound 1 as a purple red solid Yield 460 mg (19) 1H NMR (400 MHz CDCl3) δ

1032 (s 2H) 941 (t J = 47 Hz 4H) 925 (d J = 46 Hz 2H) 902 (d J = 46 Hz 2H) 849 (d J

= 80 Hz 2H) 836 (d J = 80 Hz 2H) 806 (d J = 83 Hz 2H) 745ndash730 (m 6H) 699 (d J =

88 Hz 4H) 414 (s 3H) 401 (t J = 65 Hz 4H) 189ndash177 (m 4H) 155ndash145 (m 4H)

143ndash125 (m 16H) 098ndash086 (m 6H) ndash305 (s 2H) 13C NMR (101 MHz CDCl3) δ 16764

15607 14884 14786 14688 14657 14541 14526 14090 13598 13509 13280 13215

13173 13164 13063 12966 12839 12743 12047 11845 11731 11572 10562 6856

5267 3206 2963 2949 2635 2290 1434 HRMS (MALDI-TOF) mz [M+H]+ calcd for

C62H66N5O4 9445109 found 9445108 FT-IR (KBr) νmax 3271 3038 2925 2854 1719 1603

1504 1278 1240 1108 cm-1

Synthesis of compound 2 Porphyrin 1 (943 mg 10 mmol) was dissolved in CH2Cl2MeOH

(vv = 91 200 mL) and NBS (196 mg 11 mmol) was added The reaction mixture was stirred

under air at room temperature for 15 min and quenched with acetone (10 mL) The solvent was

evaporated After evaporation of the solvent the product was isolated by column chromatography

(silica gel) using CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red

solid Yield 562 mg (55) 1H NMR (400 MHz CDCl3) δ 1016 (s 1H) 974 (t J = 43 Hz 2H)

929 (t J = 54 Hz 2H) 912 (t J = 51 Hz 2H) 887 (t J = 40 Hz 2H) 847 (d J = 80 Hz 2H)

829 (d J = 80 Hz 2H) 798 (d J = 83 Hz 2H) 737 (d J = 88 Hz 4H) 732 (d J = 83 Hz

2H) 698 (d J = 88 Hz 4H) 413 (s 3H) 400 (t J = 65 Hz 4H) 189ndash174 (m 4H) 154ndash144

(m 4H) 143ndash120 (m 16H) 089 (t J = 66 Hz 6H) ndash297 (s 2H) 13C NMR (101 MHz CDCl3)

δ 16732 15594 14877 14629 14058 13568 13469 13248 12967 12811 12731 12150

11824 11790 11553 10571 10379 6835 5249 3186 2943 2942 2929 2614 2270

1414 HRMS (MALDI-TOF) mz [M+H]+ calcd for C62H65BrN5O4 10224214 found

10224216 FT-IR (KBr) νmax 3301 3038 2925 2855 1718 1603 1504 1279 1239 1109 cm-1

Synthesis of compound 3 A 100 mL round bottom flask containing porphyrin 2 (133 mg

013 mmol) phenylboronic acid (50 mg 041 mmol) Pd(PPh3)4 (18 mg 0016 mmol) and Cs2CO3

(251 mg 077 mmol) was evacuated and flushed with nitrogen three times TolueneDMF (vv =

51 60 mL) was added The reaction mixture was heated to 90 oC for 8 h with vigorous stirring

After addition of water and dichloromethane the organic phase was separated the aqueous layer

was extracted three times with CH2Cl2 and the combined organic layer was dried over MgSO4

and filtered Then Zn(OAc)22H2O (283 mg 129 mmol) in CH3OH (10 mL) was added the

mixture was stirred at room temperature for 05 h Then the solvent was removed under reduced

pressure After addition of water and dichloromethane the organic phase was separated the

aqueous layer was extracted three times with CH2Cl2 the combined organic layer was dried over

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MgSO4 and filtered The product was isolated by column chromatography (silica gel) using

CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red solid Yield 118 mg

(84) 1H NMR (400 MHz CDCl3) δ 1022 (s 1H) 939 (dd J = 91 45 Hz 2H) 926 (d J =

45 Hz 1H) 916 (d J = 46 Hz 1H) 908ndash894 (m 3H) 891 (d J = 46 Hz 1H) 843 (d J = 81

Hz 2H) 831 (d J = 80 Hz 2H) 822 (d J = 63 Hz 2H) 801 (d J = 84 Hz 2H) 785ndash768 (m

3H) 737 (d J = 89 Hz 4H) 731 (d J = 84 Hz 2H) 696 (d J = 89 Hz 4H) 410 (s 3H) 399

(t J = 65 Hz 4H) 189ndash173 (m 4H) 149ndash143 (m 4H) 141ndash119 (m 16H) 099ndash078 (m 6H) 13C NMR (101 MHz CDCl3) δ 16743 15570 15064 15062 14989 14971 14970 14965

14951 14835 14770 14286 14080 13534 13454 13444 13401 13300 13227 13198

13194 13163 13126 12922 12779 12753 12710 12652 12160 12156 11871 11795

11546 10594 6832 5238 3184 2940 2938 2927 2611 2268 1412 HRMS

(MALDI-TOF) mz [M+H]+ calcd for C68H68N5O4Zn 10824557 found 10824535 FT-IR (KBr)

νmax 3035 2925 2854 1723 1603 1502 1276 1238 997 cm-1

Synthesis of compound 4 To a degassed solution of porphyrin 3 (271 mg 025 mmol) in

CH2Cl2 (100 ml) was added PIFA (55 mg 013 mmol) The mixture was stirred at room

temperature for 1 min The resulting yellow-brown mixture was then washed with water dried

with anhydrous Na2SO4 filtered and concentrated in vacuo The residue was purified by flash

column chromatography (silica gel CH2Cl2) to give 4 as a black solid Yield 219 mg (82) 1H

NMR (400 MHz CDCl3) δ 917 (d J = 47 Hz 2H) 903 (t J = 48 Hz 4H) 891 (d J = 47 Hz

2H) 883 (d J = 47 Hz 2H) 858 (d J = 47 Hz 2H) 836ndash823 (m 12H) 817ndash807 (m 4H)

804ndash793 (m 4H) 788ndash775 (m 6H) 725ndash715 (m 12H) 685 (d J = 89 Hz 8H) 394 (s 6H)

390 (t J = 65 Hz 8H) 181ndash167 (m 8H) 147ndash137 (m 8H) 133ndash119 (m 32H) 090ndash081 (m

12H) 13C NMR (101 MHz CDCl3) δ 16729 15562 15501 15480 15121 15032 15026

15006 15003 14923 14827 14772 14285 14070 13518 13511 13450 13440 13414

13404 13388 13242 13234 13228 13210 13140 13128 12916 12769 12764 12699

12665 12295 12201 12008 11959 11784 11537 6826 5226 3181 2936 2934 2923

2607 2265 1410 HRMS (MALDI-TOF) mz [M+H]+ calcd for C136H133N10O8Zn2 21618885

found 21618862 FT-IR (KBr) νmax 3037 2925 2854 1725 1604 1503 1320 1271 1000 cm-1

Synthesis of compound JY07 A mixture of porphyrin 4 (65 mg 003 mmol) and KOH (056

g 10 mmol) in THFEtOHH2O (1101 50 ml) was refluxed for 12 h The mixture was then

cooled to room temperature acidified with 01 M HCl to PH = 5 50 mL CH2Cl2 was added The

organic phase was separated the aqueous layer was extracted three times with CH2Cl2 and the

combined organic layer was dried over MgSO4 and filtered The residue was purified by flash

column chromatography (silica gel CH2Cl2CH3OH=51) to give 5 as a black solid Yield 60 mg

(94) 1H NMR (400 MHz THF-d8) δ 1148 (s 2H) 893 (d J = 46 Hz 2H) 879 (dd J = 46

21 Hz 4H) 873 (d J = 47 Hz 2H) 860 (d J = 47 Hz 2H) 836 (d J = 47 Hz 2H) 827ndash810

(m 12H) 797 (d J = 47 Hz 2H) 788ndash785 (m 6H) 776ndash758 (m 6H) 718ndash699 (m 12H)

675 (d J = 90 Hz 8H) 388 (t J = 63 Hz 8H) 150ndash136 (m 8H) 136ndash112 (m 40H)

090ndash076 (m 12H) 13C NMR (101 MHz THFndashd8) δ 16798 15711 15615 15603 15204

15116 15113 15103 15096 15022 14937 14923 14482 14184 13619 13612 13593

13561 13540 13473 13445 13265 13256 13238 13228 13173 13159 13096 12863

12834 12803 12740 12338 12228 12093 11843 11624 6889 3297 3051 3041 2723

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2370 1459 1458 HRMS (MALDI-TOF) mz [M+H]+ calcd for C134H129N10O8Zn2 21338572

found 21338523 FT-IR (KBr) νmax 3038 2926 2856 1731 1694 1603 1502 1237 1000 cm-1

Anal Calcd For C134H128N10O8Zn2 C 7530 H 604 N 655 Found C 7511 H 631 N 629

Synthesis of compound 5 Porphyrin 1 (400 mg 042 mmol) was dissolved in CH2Cl2MeOH

(vv = 91 150 mL) and NBS (150 mg 085 mmol) was added The reaction mixture was stirred

under air at room temperature for 15 min and quenched with acetone (10 mL) The solvent was

evaporated After evaporation of the solvent the product was isolated by column chromatography

(silica gel) using CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red

solid Yield 037 g (80) 1H NMR (400 MHz CDCl3) δ 962 (t J = 44 Hz 4H) 901 (d J = 45

Hz 2H) 875 (d J = 41 Hz 2H) 845 (d J = 81 Hz 2H) 824 (d J = 78 Hz 2H) 792 (d J =

84 Hz 2H) 737 (d J = 89 Hz 4H) 729 (d J = 85 Hz 2H) 699 (d J = 89 Hz 4H) 413 (s

3H) 401 (t J = 65 Hz 4H) 189ndash173 (m 4H) 152ndash144 (m 4H) 143ndash121 (m 16H)

097ndash079 (m 6H) -269 (s 2H) 13C NMR (101 MHz CDCl3) δ 16742 15624 14913 14645

14070 13580 13473 13262 13008 12825 12759 12293 11956 11782 11578 10412

6858 5270 3206 2963 2949 2635 2290 1433 HRMS (MALDI-TOF) mz [M+H]+ calcd

for C62H64Br2N5O4 11003320 found 11003335 FT-IR (KBr) νmax 3322 3038 2924 2855

1723 1602 1503 1278 1240 1108 cm-1

Synthesis of compound 6 A 100 mL round bottom flask containing porphyrin 5 (143 mg 013

mmol) phenylboronic acid (100 mg 082 mmol) Pd(PPh3)4 (18 mg 0016 mmol) and Cs2CO3

(251 mg 077 mmol) was evacuated and flushed with nitrogen three times TolueneDMF (vv =

51 60 mL) was added The reaction mixture was heated to 90 oC for 8 h with vigorous stirring

After addition of water and dichloromethane the organic phase was separated the aqueous layer

was extracted three times with CH2Cl2 and the combined organic layer was dried over MgSO4

and filtered Then Zn(OAc)22H2O (283 mg 129 mmol) in CH3OH (10 mL) was added the

mixture was stirred at room temperature for 05 h Then the solvent was removed under reduced

pressure After addition of water and dichloromethane the organic phase was separated the

aqueous layer was extracted three times with CH2Cl2 the combined organic layer was dried over

MgSO4 and filtered The product was isolated by column chromatography (silica gel) using

CH2Cl2 as eluent Recrystallization from CH2Cl2CH3OH gave a red solid Yield 115 mg (76) 1H NMR (400 MHz CDCl3) δ 912 (d J = 46 Hz 2H) 896 (t 4H) 887 (d J = 47 Hz 2H)

842 (d J = 82 Hz 2H) 830 (d J = 80 Hz 2H) 822 (d J = 64 Hz 4H) 799 (d J = 84 Hz

2H) 784ndash767 (m 6H) 735 (d J = 88 Hz 4H) 729 (d J = 84 Hz 2H) 695 (d J = 89 Hz

4H) 410 (s 3H) 398 (t J = 65 Hz 4H) 187ndash171 (m 4H) 152ndash142 (m 4H) 141ndash116 (m

16H) 089 (t J = 66 Hz 6H) 13C NMR (101 MHz CDCl3) δ 16764 15595 15094 15054

15030 14982 14858 14805 14299 14101 13546 13466 13435 13262 13249 13214

13161 12952 12799 12776 12733 12679 12237 12147 11948 11807 11569 6855

5259 3205 2962 2948 2634 2289 1433 HRMS (MALDI-TOF) mz [M]+ calcd for

C74H71N5O4Zn 11574792 found 11574798 FT-IR (KBr) νmax 3042 2926 2855 1725 1603

1502 1278 1237 1001 cm-1

Synthesis of compound JY06 A mixture of porphyrin 6 (127 mg 011 mmol) and KOH

(056 g 10 mmol) in THFEtOHH2O (1101 50 ml) was refluxed for 12 h The mixture was

S7

then cooled to room temperature acidified with 01 M HCl to PH = 5 50 mL CH2Cl2 was added

The solution was washed three times with water and the combined organic layer was dried with

MgSO4 and removed by vacuo The residue was purified by flash column chromatography (silica

gel CH2Cl2CH3OH=101) to give JY06 as a red solid Yield 110 mg (87) 1H NMR (400 MHz

THF) δ 1164 (s 1H) 901 (d J = 46 Hz 2H) 891ndash873 (m 6H) 842 (d J = 81 Hz 2H) 829

(d J = 81 Hz 2H) 826ndash811 (m 4H) 798 (d J = 85 Hz 2H) 786ndash764 (m 6H) 742ndash718 (m

6H) 696 (d J = 90 Hz 4H) 399 (t J = 64 Hz 4H) 188ndash174 (m 4H) 160ndash145 (m 4H)

144ndash121 (m 16H) 102ndash076 (m 6H) 13C NMR (101 MHz THF) δ 16807 15721 15164

15123 15104 15067 14949 14925 14473 14193 13633 13593 13555 13547 13274

13261 13222 13191 13104 12871 12827 12815 12734 12256 12171 12008 11851

11635 6898 3300 3056 3054 3044 2728 2373 1460 HRMS (MALDI-TOF) mz [M]+

calcd for C73H69N5O4Zn 11434636 found 11434638 FT-IR (KBr) νmax 3041 2925 2854 1734

1693 1604 1502 1237 1001 cm-1 Anal Calcd For C73H69N5O4Zn C 7653 H 607 N 611

Found C 7639 H 602 N 609

S8

Fig S1 Fluorescence spectra of JY06 and JY07 in THF

Fig S2 Frontier orbitals of JY06 and JY07 (HOMO and LUMO)

Fig S3 FTIR spectra of (a) JY06 and (b) JY07 powders and stained TiO2 films

Fig S4 The photocurrent density-voltage (J-V) curves based on JY07 with and without CDCA

S9

Table S1 Photovoltaic performance for DSSCs based on JY07

dye CDCA (mM) Voc (V) Jsc (mAcm2) FF η () Γ (nmol cm-2)

JY07 0 065 1320 062 533 62

JY07 10 065 1220 061 485 45 aActive area 016 cm2 Electrolyte is composed of 03 M 12-dimethyl-3-propylimidazolium iodide (DMPII) 01

M LiI 005 M I2 and 05 M 4-tert -butyl pyridine in acetonitrile

Photostability study The long-term stability of DSSCs is a critical requirement for their photovoltaic application We

have used a straightforward method reported in literature to examine the stability of studied dyes5 For the stability study TiO2 thin films with areas of 1times1 cm2 and thicknesses of 3-4 μm were used

The films were immersed in a 03 mM solution of the porphyrin in THF for 05 h dried and the

absorbance was measured Then the same films were irradiated under standard one-sun

illumination for 5 min and 30 min and the absorbance was measured again

Fig S5 Absorption spectra of (a) JY06 and (b) JY07 that were adsorbed onto TiO2 films after

irradiation for 0 5 and 30 min

Fig S6 EIS spectra of DSSCs tested at -06 V forward bias in the dark (a) Nyquist and (b) Bode

phase plots

S10

References (1) J-W Ka and C-H Lee Tetrahedron Lett 2000 41 4609

(2) M Yoshida T Doi S Kang J Watanabe and T Takahashi Chem Commun 2009 2756

(3) J Mao N He Z Ning Q Zhang F Guo L Chen W Wu J Hua and H Tian Angew Chem

Int Ed 2012 51 9873

(4) Y Y Dou G R Li J Song and X P Gao Phys Chem Chem Phys 2012 14 1339

(5) (a) R B Ambre G-F Chang and C-H Hung Chem Commun 2014 50 725 (b) Y Wu M

Marszalek S M Zakeeruddin Q Zhang H Tian M Graumltzel and W Zhu Energy Environ

Sci 2012 5 8261 (c) R Katoh A Furube S Mori M Miyashita K Sunahara N Koumura

and K Hara Energy Environ Sci 2009 2 542

S11

1H NMR and 13C NMR spectra

Fig S7 1H NMR spectrum of compound 1 in CDCl3

Fig S8 13C NMR spectrum of compound 1 in CDCl3

S12

Fig S9 1H NMR spectrum of compound 2 in CDCl3

Fig S10 13C NMR spectrum of compound 2 in CDCl3

S13

Fig S11 1H NMR spectrum of compound 3 in CDCl3

Fig S12 13C NMR spectrum of compound 3 in CDCl3

S14

Fig S13 1H NMR spectrum of compound 4 in CDCl3

Fig S14 13C NMR spectrum of compound 4 in CDCl3

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 2: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S2

General All solvents were purified according to standard methods Other chemicals (AR) obtained from

commercial sources were used without further purification NMR solvents were used as received 1H NMR and 13C NMR spectra were recorded on Bruker 400 MHz spectrometer using TMS as the

internal standard UV-vis spectra were obtained on a Varian Cary 300 Conc UV-visible

spectrophotometer HR-MS data was measured on a Varian 70T FTMS IR spectra were recorded

on a Bio-rad FTS6000 spectrometer Elementary analyses were performed using a Vario EL CUBE

Analyzer Cyclic voltammetry experiments and electrochemical impedance spectroscopy were

recorded on a Zennium electrochemical workstation (Zahner Germany) Electrochemical

impedance spectroscopy was recorded in the dark under -060 V bias The frequencies explored

ranged from 100 mHz to 100 kHz Cyclic voltammetry experiments were carried out using a

conventional three-electrode system employing glassy carbon electrode as the working electrode

AgAg+ electrode as the reference electrode and Pt wire as the counter electrode The redox

potentials were measured in THF using 01 M n-Bu4NPF6 as supporting electrolyte with a scan

rate of 100 mV S-1 Dipyrromethane1 4-Octyloxyiodobenzene2

NN-bis(4-octyloxyphenyl)aniline2 4-(bis(4-(octyloxy)phenyl)amino)benzaldehyde3 were

synthesized according to literature methods

Fabrication and characterization of DSSCs The DSSCs were fabricated according to a previous literature procedure4 A TiO2 film (~10 microm)

for the transparent nanocrystalline layer was prepared by doctor-blade method coating a

commercial 20 nm TiO2 sol (China National Academy of Nanotechnology amp Engineering) onto

the treated FTO conductive glass (Nippon Sheet Glass Japan fluorine-doped SnO2 over layer

sheet resistance of 15 Ωsq treated with TiCl4 (005 M) solution) The scattering layer (~4 microm)

was applied over the transparent layer by doctor-blade method then gradually heated to 500degC

and sintered for 60 min The resulting TiO2 electrodes were treated by TiCl4 and sintered again at

500degC for 60 min The Pt electrode was obtained by thermal deposition of a platinum layer onto

the surface of FTO at 450degC for 30 min The TiO2 thin film was dipped into the 03 mM dye

solution in THF for at least 12 h The electrolyte was composed of 03 M DMPII 01 M LiI 005

M I2 and 05 M 4-tert-butylpyridine in acetonitrile The DSSCs were illuminated by a solar

simulator (Orielreg Sol2A Newport Corporation) under 100 mWcm2 irradiation which was

calibrated by a standard silicon solar cell The photocurrent intensity-voltage (J-V) characteristic

curves of the DSSC under simulated sunlight were recorded using an IM6ex electrochemical

workstation (Zahner Germany) The measurement of the incident photon-to-current conversion

efficiency (IPCE) was performed by using a commercial setup (QTest Station 2000 IPCE

Measurement System CROWNTECH USA)

Optical Spectroscopy UVVis absorption spectra of the porphyrins in THF and adsorbed onto TiO2 electrodes were

recorded on a Varian Cary 300 Conc UV-visible spectrophotometer For the absorption spectra of

the thin films on TiO2 TiO2 films (area 1times1 cm2) were prepared with thicknesses of about 1μm to

obtain comparable shapes and peak positions The films were immersed in 03 mM solutions of

the porphyrins in THF for 5 minutes and the films were rinsed with THF dried and the

absorbance was measured (Transmittance UV spectra) Steady-state fluorescence spectra were

S3

acquired on a Varian Cary Eclipse fluorescence spectrophotometer

Dye-loading examination To determine the dye-loading amount of JY06 and JY07 on TiO2 films the dye adsorbed on TiO2

(04 cm times 04 cm) was desorbed in 02 M KOH (aq) in THF (28 vv) The calibration curves for

JY06 and JY07 in 02 M KOH (aq) in THF (28 vv) were derived to obtain the absorption

coefficients The amounts of dye-loading on TiO2 films were obtained from the measured

absorbances of the Soret bands in the spectra and the calibrated absorption coefficients at the same

spectral position according to Beersrsquo law

In fact more than 12 h exposure to commonly used 01 M aqueous solution of KOH in THF (28

vv) was unable to completely desorb the dye JY07 from TiO2 Instead a 02 M aqueous solution

of KOH in THF (28 vv) was used to desorb the dye from TiO2 The requirement of a higher

concentration of the base to desorb the dye from TiO2 provides further evidence of a stronger

adhesion of the double D-π-A dye than the porphyrin dye that possessed a single anchoring group

Synthetic procedure

Reagents (i) TFA DDQ (ii) NBS (iii) a) Phenylboronic acid Pd(PPh3)4 Cs2CO3 b)

Zn(OAc)22H2O (iv) PIFA (v) KOH EtOHH2OTHF

N

NH N

HN

NR R

Br Br

COOCH3

N

N N

N

NR R

COOCH3

ZnN

N N

N

NR R

COOH

ZnN

NH N

HN

NR R

COOCH31 5 6 JY06

(i) (ii) (iii)

R=

OC8H17

Reagents (i) NBS (ii) a) Phenylboronic acid Pd(PPh3)4 Cs2CO3 b) Zn(OAc)22H2O (iii) KOH

EtOHH2OTHF

S4

Scheme S1 Syntheses of JY06 and JY07

Synthesis of compound 1 To a degassed solution of dipyrromethane (731 mg 5 mmol)

4-(bis(4-(octyloxy)phenyl)amino)benzaldehyde (132 g 25 mmol) and methyl 4-formylbenzoate

(4105 mg 25 mmol) in CH2Cl2 (500 mL) was added CF3COOH (022 mL 3 mmol) The mixture

was stirred in the dark for 10 h and then DDQ (10 g 45mmol) was added After another 1 h

Et3N (50 mL) was added and the solvent was removed under reduced pressure Purification by

silica gel column chromatography (CH2Cl2PE = 31) and recrystallization from CH2Cl2MeOH

afforded compound 1 as a purple red solid Yield 460 mg (19) 1H NMR (400 MHz CDCl3) δ

1032 (s 2H) 941 (t J = 47 Hz 4H) 925 (d J = 46 Hz 2H) 902 (d J = 46 Hz 2H) 849 (d J

= 80 Hz 2H) 836 (d J = 80 Hz 2H) 806 (d J = 83 Hz 2H) 745ndash730 (m 6H) 699 (d J =

88 Hz 4H) 414 (s 3H) 401 (t J = 65 Hz 4H) 189ndash177 (m 4H) 155ndash145 (m 4H)

143ndash125 (m 16H) 098ndash086 (m 6H) ndash305 (s 2H) 13C NMR (101 MHz CDCl3) δ 16764

15607 14884 14786 14688 14657 14541 14526 14090 13598 13509 13280 13215

13173 13164 13063 12966 12839 12743 12047 11845 11731 11572 10562 6856

5267 3206 2963 2949 2635 2290 1434 HRMS (MALDI-TOF) mz [M+H]+ calcd for

C62H66N5O4 9445109 found 9445108 FT-IR (KBr) νmax 3271 3038 2925 2854 1719 1603

1504 1278 1240 1108 cm-1

Synthesis of compound 2 Porphyrin 1 (943 mg 10 mmol) was dissolved in CH2Cl2MeOH

(vv = 91 200 mL) and NBS (196 mg 11 mmol) was added The reaction mixture was stirred

under air at room temperature for 15 min and quenched with acetone (10 mL) The solvent was

evaporated After evaporation of the solvent the product was isolated by column chromatography

(silica gel) using CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red

solid Yield 562 mg (55) 1H NMR (400 MHz CDCl3) δ 1016 (s 1H) 974 (t J = 43 Hz 2H)

929 (t J = 54 Hz 2H) 912 (t J = 51 Hz 2H) 887 (t J = 40 Hz 2H) 847 (d J = 80 Hz 2H)

829 (d J = 80 Hz 2H) 798 (d J = 83 Hz 2H) 737 (d J = 88 Hz 4H) 732 (d J = 83 Hz

2H) 698 (d J = 88 Hz 4H) 413 (s 3H) 400 (t J = 65 Hz 4H) 189ndash174 (m 4H) 154ndash144

(m 4H) 143ndash120 (m 16H) 089 (t J = 66 Hz 6H) ndash297 (s 2H) 13C NMR (101 MHz CDCl3)

δ 16732 15594 14877 14629 14058 13568 13469 13248 12967 12811 12731 12150

11824 11790 11553 10571 10379 6835 5249 3186 2943 2942 2929 2614 2270

1414 HRMS (MALDI-TOF) mz [M+H]+ calcd for C62H65BrN5O4 10224214 found

10224216 FT-IR (KBr) νmax 3301 3038 2925 2855 1718 1603 1504 1279 1239 1109 cm-1

Synthesis of compound 3 A 100 mL round bottom flask containing porphyrin 2 (133 mg

013 mmol) phenylboronic acid (50 mg 041 mmol) Pd(PPh3)4 (18 mg 0016 mmol) and Cs2CO3

(251 mg 077 mmol) was evacuated and flushed with nitrogen three times TolueneDMF (vv =

51 60 mL) was added The reaction mixture was heated to 90 oC for 8 h with vigorous stirring

After addition of water and dichloromethane the organic phase was separated the aqueous layer

was extracted three times with CH2Cl2 and the combined organic layer was dried over MgSO4

and filtered Then Zn(OAc)22H2O (283 mg 129 mmol) in CH3OH (10 mL) was added the

mixture was stirred at room temperature for 05 h Then the solvent was removed under reduced

pressure After addition of water and dichloromethane the organic phase was separated the

aqueous layer was extracted three times with CH2Cl2 the combined organic layer was dried over

S5

MgSO4 and filtered The product was isolated by column chromatography (silica gel) using

CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red solid Yield 118 mg

(84) 1H NMR (400 MHz CDCl3) δ 1022 (s 1H) 939 (dd J = 91 45 Hz 2H) 926 (d J =

45 Hz 1H) 916 (d J = 46 Hz 1H) 908ndash894 (m 3H) 891 (d J = 46 Hz 1H) 843 (d J = 81

Hz 2H) 831 (d J = 80 Hz 2H) 822 (d J = 63 Hz 2H) 801 (d J = 84 Hz 2H) 785ndash768 (m

3H) 737 (d J = 89 Hz 4H) 731 (d J = 84 Hz 2H) 696 (d J = 89 Hz 4H) 410 (s 3H) 399

(t J = 65 Hz 4H) 189ndash173 (m 4H) 149ndash143 (m 4H) 141ndash119 (m 16H) 099ndash078 (m 6H) 13C NMR (101 MHz CDCl3) δ 16743 15570 15064 15062 14989 14971 14970 14965

14951 14835 14770 14286 14080 13534 13454 13444 13401 13300 13227 13198

13194 13163 13126 12922 12779 12753 12710 12652 12160 12156 11871 11795

11546 10594 6832 5238 3184 2940 2938 2927 2611 2268 1412 HRMS

(MALDI-TOF) mz [M+H]+ calcd for C68H68N5O4Zn 10824557 found 10824535 FT-IR (KBr)

νmax 3035 2925 2854 1723 1603 1502 1276 1238 997 cm-1

Synthesis of compound 4 To a degassed solution of porphyrin 3 (271 mg 025 mmol) in

CH2Cl2 (100 ml) was added PIFA (55 mg 013 mmol) The mixture was stirred at room

temperature for 1 min The resulting yellow-brown mixture was then washed with water dried

with anhydrous Na2SO4 filtered and concentrated in vacuo The residue was purified by flash

column chromatography (silica gel CH2Cl2) to give 4 as a black solid Yield 219 mg (82) 1H

NMR (400 MHz CDCl3) δ 917 (d J = 47 Hz 2H) 903 (t J = 48 Hz 4H) 891 (d J = 47 Hz

2H) 883 (d J = 47 Hz 2H) 858 (d J = 47 Hz 2H) 836ndash823 (m 12H) 817ndash807 (m 4H)

804ndash793 (m 4H) 788ndash775 (m 6H) 725ndash715 (m 12H) 685 (d J = 89 Hz 8H) 394 (s 6H)

390 (t J = 65 Hz 8H) 181ndash167 (m 8H) 147ndash137 (m 8H) 133ndash119 (m 32H) 090ndash081 (m

12H) 13C NMR (101 MHz CDCl3) δ 16729 15562 15501 15480 15121 15032 15026

15006 15003 14923 14827 14772 14285 14070 13518 13511 13450 13440 13414

13404 13388 13242 13234 13228 13210 13140 13128 12916 12769 12764 12699

12665 12295 12201 12008 11959 11784 11537 6826 5226 3181 2936 2934 2923

2607 2265 1410 HRMS (MALDI-TOF) mz [M+H]+ calcd for C136H133N10O8Zn2 21618885

found 21618862 FT-IR (KBr) νmax 3037 2925 2854 1725 1604 1503 1320 1271 1000 cm-1

Synthesis of compound JY07 A mixture of porphyrin 4 (65 mg 003 mmol) and KOH (056

g 10 mmol) in THFEtOHH2O (1101 50 ml) was refluxed for 12 h The mixture was then

cooled to room temperature acidified with 01 M HCl to PH = 5 50 mL CH2Cl2 was added The

organic phase was separated the aqueous layer was extracted three times with CH2Cl2 and the

combined organic layer was dried over MgSO4 and filtered The residue was purified by flash

column chromatography (silica gel CH2Cl2CH3OH=51) to give 5 as a black solid Yield 60 mg

(94) 1H NMR (400 MHz THF-d8) δ 1148 (s 2H) 893 (d J = 46 Hz 2H) 879 (dd J = 46

21 Hz 4H) 873 (d J = 47 Hz 2H) 860 (d J = 47 Hz 2H) 836 (d J = 47 Hz 2H) 827ndash810

(m 12H) 797 (d J = 47 Hz 2H) 788ndash785 (m 6H) 776ndash758 (m 6H) 718ndash699 (m 12H)

675 (d J = 90 Hz 8H) 388 (t J = 63 Hz 8H) 150ndash136 (m 8H) 136ndash112 (m 40H)

090ndash076 (m 12H) 13C NMR (101 MHz THFndashd8) δ 16798 15711 15615 15603 15204

15116 15113 15103 15096 15022 14937 14923 14482 14184 13619 13612 13593

13561 13540 13473 13445 13265 13256 13238 13228 13173 13159 13096 12863

12834 12803 12740 12338 12228 12093 11843 11624 6889 3297 3051 3041 2723

S6

2370 1459 1458 HRMS (MALDI-TOF) mz [M+H]+ calcd for C134H129N10O8Zn2 21338572

found 21338523 FT-IR (KBr) νmax 3038 2926 2856 1731 1694 1603 1502 1237 1000 cm-1

Anal Calcd For C134H128N10O8Zn2 C 7530 H 604 N 655 Found C 7511 H 631 N 629

Synthesis of compound 5 Porphyrin 1 (400 mg 042 mmol) was dissolved in CH2Cl2MeOH

(vv = 91 150 mL) and NBS (150 mg 085 mmol) was added The reaction mixture was stirred

under air at room temperature for 15 min and quenched with acetone (10 mL) The solvent was

evaporated After evaporation of the solvent the product was isolated by column chromatography

(silica gel) using CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red

solid Yield 037 g (80) 1H NMR (400 MHz CDCl3) δ 962 (t J = 44 Hz 4H) 901 (d J = 45

Hz 2H) 875 (d J = 41 Hz 2H) 845 (d J = 81 Hz 2H) 824 (d J = 78 Hz 2H) 792 (d J =

84 Hz 2H) 737 (d J = 89 Hz 4H) 729 (d J = 85 Hz 2H) 699 (d J = 89 Hz 4H) 413 (s

3H) 401 (t J = 65 Hz 4H) 189ndash173 (m 4H) 152ndash144 (m 4H) 143ndash121 (m 16H)

097ndash079 (m 6H) -269 (s 2H) 13C NMR (101 MHz CDCl3) δ 16742 15624 14913 14645

14070 13580 13473 13262 13008 12825 12759 12293 11956 11782 11578 10412

6858 5270 3206 2963 2949 2635 2290 1433 HRMS (MALDI-TOF) mz [M+H]+ calcd

for C62H64Br2N5O4 11003320 found 11003335 FT-IR (KBr) νmax 3322 3038 2924 2855

1723 1602 1503 1278 1240 1108 cm-1

Synthesis of compound 6 A 100 mL round bottom flask containing porphyrin 5 (143 mg 013

mmol) phenylboronic acid (100 mg 082 mmol) Pd(PPh3)4 (18 mg 0016 mmol) and Cs2CO3

(251 mg 077 mmol) was evacuated and flushed with nitrogen three times TolueneDMF (vv =

51 60 mL) was added The reaction mixture was heated to 90 oC for 8 h with vigorous stirring

After addition of water and dichloromethane the organic phase was separated the aqueous layer

was extracted three times with CH2Cl2 and the combined organic layer was dried over MgSO4

and filtered Then Zn(OAc)22H2O (283 mg 129 mmol) in CH3OH (10 mL) was added the

mixture was stirred at room temperature for 05 h Then the solvent was removed under reduced

pressure After addition of water and dichloromethane the organic phase was separated the

aqueous layer was extracted three times with CH2Cl2 the combined organic layer was dried over

MgSO4 and filtered The product was isolated by column chromatography (silica gel) using

CH2Cl2 as eluent Recrystallization from CH2Cl2CH3OH gave a red solid Yield 115 mg (76) 1H NMR (400 MHz CDCl3) δ 912 (d J = 46 Hz 2H) 896 (t 4H) 887 (d J = 47 Hz 2H)

842 (d J = 82 Hz 2H) 830 (d J = 80 Hz 2H) 822 (d J = 64 Hz 4H) 799 (d J = 84 Hz

2H) 784ndash767 (m 6H) 735 (d J = 88 Hz 4H) 729 (d J = 84 Hz 2H) 695 (d J = 89 Hz

4H) 410 (s 3H) 398 (t J = 65 Hz 4H) 187ndash171 (m 4H) 152ndash142 (m 4H) 141ndash116 (m

16H) 089 (t J = 66 Hz 6H) 13C NMR (101 MHz CDCl3) δ 16764 15595 15094 15054

15030 14982 14858 14805 14299 14101 13546 13466 13435 13262 13249 13214

13161 12952 12799 12776 12733 12679 12237 12147 11948 11807 11569 6855

5259 3205 2962 2948 2634 2289 1433 HRMS (MALDI-TOF) mz [M]+ calcd for

C74H71N5O4Zn 11574792 found 11574798 FT-IR (KBr) νmax 3042 2926 2855 1725 1603

1502 1278 1237 1001 cm-1

Synthesis of compound JY06 A mixture of porphyrin 6 (127 mg 011 mmol) and KOH

(056 g 10 mmol) in THFEtOHH2O (1101 50 ml) was refluxed for 12 h The mixture was

S7

then cooled to room temperature acidified with 01 M HCl to PH = 5 50 mL CH2Cl2 was added

The solution was washed three times with water and the combined organic layer was dried with

MgSO4 and removed by vacuo The residue was purified by flash column chromatography (silica

gel CH2Cl2CH3OH=101) to give JY06 as a red solid Yield 110 mg (87) 1H NMR (400 MHz

THF) δ 1164 (s 1H) 901 (d J = 46 Hz 2H) 891ndash873 (m 6H) 842 (d J = 81 Hz 2H) 829

(d J = 81 Hz 2H) 826ndash811 (m 4H) 798 (d J = 85 Hz 2H) 786ndash764 (m 6H) 742ndash718 (m

6H) 696 (d J = 90 Hz 4H) 399 (t J = 64 Hz 4H) 188ndash174 (m 4H) 160ndash145 (m 4H)

144ndash121 (m 16H) 102ndash076 (m 6H) 13C NMR (101 MHz THF) δ 16807 15721 15164

15123 15104 15067 14949 14925 14473 14193 13633 13593 13555 13547 13274

13261 13222 13191 13104 12871 12827 12815 12734 12256 12171 12008 11851

11635 6898 3300 3056 3054 3044 2728 2373 1460 HRMS (MALDI-TOF) mz [M]+

calcd for C73H69N5O4Zn 11434636 found 11434638 FT-IR (KBr) νmax 3041 2925 2854 1734

1693 1604 1502 1237 1001 cm-1 Anal Calcd For C73H69N5O4Zn C 7653 H 607 N 611

Found C 7639 H 602 N 609

S8

Fig S1 Fluorescence spectra of JY06 and JY07 in THF

Fig S2 Frontier orbitals of JY06 and JY07 (HOMO and LUMO)

Fig S3 FTIR spectra of (a) JY06 and (b) JY07 powders and stained TiO2 films

Fig S4 The photocurrent density-voltage (J-V) curves based on JY07 with and without CDCA

S9

Table S1 Photovoltaic performance for DSSCs based on JY07

dye CDCA (mM) Voc (V) Jsc (mAcm2) FF η () Γ (nmol cm-2)

JY07 0 065 1320 062 533 62

JY07 10 065 1220 061 485 45 aActive area 016 cm2 Electrolyte is composed of 03 M 12-dimethyl-3-propylimidazolium iodide (DMPII) 01

M LiI 005 M I2 and 05 M 4-tert -butyl pyridine in acetonitrile

Photostability study The long-term stability of DSSCs is a critical requirement for their photovoltaic application We

have used a straightforward method reported in literature to examine the stability of studied dyes5 For the stability study TiO2 thin films with areas of 1times1 cm2 and thicknesses of 3-4 μm were used

The films were immersed in a 03 mM solution of the porphyrin in THF for 05 h dried and the

absorbance was measured Then the same films were irradiated under standard one-sun

illumination for 5 min and 30 min and the absorbance was measured again

Fig S5 Absorption spectra of (a) JY06 and (b) JY07 that were adsorbed onto TiO2 films after

irradiation for 0 5 and 30 min

Fig S6 EIS spectra of DSSCs tested at -06 V forward bias in the dark (a) Nyquist and (b) Bode

phase plots

S10

References (1) J-W Ka and C-H Lee Tetrahedron Lett 2000 41 4609

(2) M Yoshida T Doi S Kang J Watanabe and T Takahashi Chem Commun 2009 2756

(3) J Mao N He Z Ning Q Zhang F Guo L Chen W Wu J Hua and H Tian Angew Chem

Int Ed 2012 51 9873

(4) Y Y Dou G R Li J Song and X P Gao Phys Chem Chem Phys 2012 14 1339

(5) (a) R B Ambre G-F Chang and C-H Hung Chem Commun 2014 50 725 (b) Y Wu M

Marszalek S M Zakeeruddin Q Zhang H Tian M Graumltzel and W Zhu Energy Environ

Sci 2012 5 8261 (c) R Katoh A Furube S Mori M Miyashita K Sunahara N Koumura

and K Hara Energy Environ Sci 2009 2 542

S11

1H NMR and 13C NMR spectra

Fig S7 1H NMR spectrum of compound 1 in CDCl3

Fig S8 13C NMR spectrum of compound 1 in CDCl3

S12

Fig S9 1H NMR spectrum of compound 2 in CDCl3

Fig S10 13C NMR spectrum of compound 2 in CDCl3

S13

Fig S11 1H NMR spectrum of compound 3 in CDCl3

Fig S12 13C NMR spectrum of compound 3 in CDCl3

S14

Fig S13 1H NMR spectrum of compound 4 in CDCl3

Fig S14 13C NMR spectrum of compound 4 in CDCl3

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 3: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S3

acquired on a Varian Cary Eclipse fluorescence spectrophotometer

Dye-loading examination To determine the dye-loading amount of JY06 and JY07 on TiO2 films the dye adsorbed on TiO2

(04 cm times 04 cm) was desorbed in 02 M KOH (aq) in THF (28 vv) The calibration curves for

JY06 and JY07 in 02 M KOH (aq) in THF (28 vv) were derived to obtain the absorption

coefficients The amounts of dye-loading on TiO2 films were obtained from the measured

absorbances of the Soret bands in the spectra and the calibrated absorption coefficients at the same

spectral position according to Beersrsquo law

In fact more than 12 h exposure to commonly used 01 M aqueous solution of KOH in THF (28

vv) was unable to completely desorb the dye JY07 from TiO2 Instead a 02 M aqueous solution

of KOH in THF (28 vv) was used to desorb the dye from TiO2 The requirement of a higher

concentration of the base to desorb the dye from TiO2 provides further evidence of a stronger

adhesion of the double D-π-A dye than the porphyrin dye that possessed a single anchoring group

Synthetic procedure

Reagents (i) TFA DDQ (ii) NBS (iii) a) Phenylboronic acid Pd(PPh3)4 Cs2CO3 b)

Zn(OAc)22H2O (iv) PIFA (v) KOH EtOHH2OTHF

N

NH N

HN

NR R

Br Br

COOCH3

N

N N

N

NR R

COOCH3

ZnN

N N

N

NR R

COOH

ZnN

NH N

HN

NR R

COOCH31 5 6 JY06

(i) (ii) (iii)

R=

OC8H17

Reagents (i) NBS (ii) a) Phenylboronic acid Pd(PPh3)4 Cs2CO3 b) Zn(OAc)22H2O (iii) KOH

EtOHH2OTHF

S4

Scheme S1 Syntheses of JY06 and JY07

Synthesis of compound 1 To a degassed solution of dipyrromethane (731 mg 5 mmol)

4-(bis(4-(octyloxy)phenyl)amino)benzaldehyde (132 g 25 mmol) and methyl 4-formylbenzoate

(4105 mg 25 mmol) in CH2Cl2 (500 mL) was added CF3COOH (022 mL 3 mmol) The mixture

was stirred in the dark for 10 h and then DDQ (10 g 45mmol) was added After another 1 h

Et3N (50 mL) was added and the solvent was removed under reduced pressure Purification by

silica gel column chromatography (CH2Cl2PE = 31) and recrystallization from CH2Cl2MeOH

afforded compound 1 as a purple red solid Yield 460 mg (19) 1H NMR (400 MHz CDCl3) δ

1032 (s 2H) 941 (t J = 47 Hz 4H) 925 (d J = 46 Hz 2H) 902 (d J = 46 Hz 2H) 849 (d J

= 80 Hz 2H) 836 (d J = 80 Hz 2H) 806 (d J = 83 Hz 2H) 745ndash730 (m 6H) 699 (d J =

88 Hz 4H) 414 (s 3H) 401 (t J = 65 Hz 4H) 189ndash177 (m 4H) 155ndash145 (m 4H)

143ndash125 (m 16H) 098ndash086 (m 6H) ndash305 (s 2H) 13C NMR (101 MHz CDCl3) δ 16764

15607 14884 14786 14688 14657 14541 14526 14090 13598 13509 13280 13215

13173 13164 13063 12966 12839 12743 12047 11845 11731 11572 10562 6856

5267 3206 2963 2949 2635 2290 1434 HRMS (MALDI-TOF) mz [M+H]+ calcd for

C62H66N5O4 9445109 found 9445108 FT-IR (KBr) νmax 3271 3038 2925 2854 1719 1603

1504 1278 1240 1108 cm-1

Synthesis of compound 2 Porphyrin 1 (943 mg 10 mmol) was dissolved in CH2Cl2MeOH

(vv = 91 200 mL) and NBS (196 mg 11 mmol) was added The reaction mixture was stirred

under air at room temperature for 15 min and quenched with acetone (10 mL) The solvent was

evaporated After evaporation of the solvent the product was isolated by column chromatography

(silica gel) using CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red

solid Yield 562 mg (55) 1H NMR (400 MHz CDCl3) δ 1016 (s 1H) 974 (t J = 43 Hz 2H)

929 (t J = 54 Hz 2H) 912 (t J = 51 Hz 2H) 887 (t J = 40 Hz 2H) 847 (d J = 80 Hz 2H)

829 (d J = 80 Hz 2H) 798 (d J = 83 Hz 2H) 737 (d J = 88 Hz 4H) 732 (d J = 83 Hz

2H) 698 (d J = 88 Hz 4H) 413 (s 3H) 400 (t J = 65 Hz 4H) 189ndash174 (m 4H) 154ndash144

(m 4H) 143ndash120 (m 16H) 089 (t J = 66 Hz 6H) ndash297 (s 2H) 13C NMR (101 MHz CDCl3)

δ 16732 15594 14877 14629 14058 13568 13469 13248 12967 12811 12731 12150

11824 11790 11553 10571 10379 6835 5249 3186 2943 2942 2929 2614 2270

1414 HRMS (MALDI-TOF) mz [M+H]+ calcd for C62H65BrN5O4 10224214 found

10224216 FT-IR (KBr) νmax 3301 3038 2925 2855 1718 1603 1504 1279 1239 1109 cm-1

Synthesis of compound 3 A 100 mL round bottom flask containing porphyrin 2 (133 mg

013 mmol) phenylboronic acid (50 mg 041 mmol) Pd(PPh3)4 (18 mg 0016 mmol) and Cs2CO3

(251 mg 077 mmol) was evacuated and flushed with nitrogen three times TolueneDMF (vv =

51 60 mL) was added The reaction mixture was heated to 90 oC for 8 h with vigorous stirring

After addition of water and dichloromethane the organic phase was separated the aqueous layer

was extracted three times with CH2Cl2 and the combined organic layer was dried over MgSO4

and filtered Then Zn(OAc)22H2O (283 mg 129 mmol) in CH3OH (10 mL) was added the

mixture was stirred at room temperature for 05 h Then the solvent was removed under reduced

pressure After addition of water and dichloromethane the organic phase was separated the

aqueous layer was extracted three times with CH2Cl2 the combined organic layer was dried over

S5

MgSO4 and filtered The product was isolated by column chromatography (silica gel) using

CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red solid Yield 118 mg

(84) 1H NMR (400 MHz CDCl3) δ 1022 (s 1H) 939 (dd J = 91 45 Hz 2H) 926 (d J =

45 Hz 1H) 916 (d J = 46 Hz 1H) 908ndash894 (m 3H) 891 (d J = 46 Hz 1H) 843 (d J = 81

Hz 2H) 831 (d J = 80 Hz 2H) 822 (d J = 63 Hz 2H) 801 (d J = 84 Hz 2H) 785ndash768 (m

3H) 737 (d J = 89 Hz 4H) 731 (d J = 84 Hz 2H) 696 (d J = 89 Hz 4H) 410 (s 3H) 399

(t J = 65 Hz 4H) 189ndash173 (m 4H) 149ndash143 (m 4H) 141ndash119 (m 16H) 099ndash078 (m 6H) 13C NMR (101 MHz CDCl3) δ 16743 15570 15064 15062 14989 14971 14970 14965

14951 14835 14770 14286 14080 13534 13454 13444 13401 13300 13227 13198

13194 13163 13126 12922 12779 12753 12710 12652 12160 12156 11871 11795

11546 10594 6832 5238 3184 2940 2938 2927 2611 2268 1412 HRMS

(MALDI-TOF) mz [M+H]+ calcd for C68H68N5O4Zn 10824557 found 10824535 FT-IR (KBr)

νmax 3035 2925 2854 1723 1603 1502 1276 1238 997 cm-1

Synthesis of compound 4 To a degassed solution of porphyrin 3 (271 mg 025 mmol) in

CH2Cl2 (100 ml) was added PIFA (55 mg 013 mmol) The mixture was stirred at room

temperature for 1 min The resulting yellow-brown mixture was then washed with water dried

with anhydrous Na2SO4 filtered and concentrated in vacuo The residue was purified by flash

column chromatography (silica gel CH2Cl2) to give 4 as a black solid Yield 219 mg (82) 1H

NMR (400 MHz CDCl3) δ 917 (d J = 47 Hz 2H) 903 (t J = 48 Hz 4H) 891 (d J = 47 Hz

2H) 883 (d J = 47 Hz 2H) 858 (d J = 47 Hz 2H) 836ndash823 (m 12H) 817ndash807 (m 4H)

804ndash793 (m 4H) 788ndash775 (m 6H) 725ndash715 (m 12H) 685 (d J = 89 Hz 8H) 394 (s 6H)

390 (t J = 65 Hz 8H) 181ndash167 (m 8H) 147ndash137 (m 8H) 133ndash119 (m 32H) 090ndash081 (m

12H) 13C NMR (101 MHz CDCl3) δ 16729 15562 15501 15480 15121 15032 15026

15006 15003 14923 14827 14772 14285 14070 13518 13511 13450 13440 13414

13404 13388 13242 13234 13228 13210 13140 13128 12916 12769 12764 12699

12665 12295 12201 12008 11959 11784 11537 6826 5226 3181 2936 2934 2923

2607 2265 1410 HRMS (MALDI-TOF) mz [M+H]+ calcd for C136H133N10O8Zn2 21618885

found 21618862 FT-IR (KBr) νmax 3037 2925 2854 1725 1604 1503 1320 1271 1000 cm-1

Synthesis of compound JY07 A mixture of porphyrin 4 (65 mg 003 mmol) and KOH (056

g 10 mmol) in THFEtOHH2O (1101 50 ml) was refluxed for 12 h The mixture was then

cooled to room temperature acidified with 01 M HCl to PH = 5 50 mL CH2Cl2 was added The

organic phase was separated the aqueous layer was extracted three times with CH2Cl2 and the

combined organic layer was dried over MgSO4 and filtered The residue was purified by flash

column chromatography (silica gel CH2Cl2CH3OH=51) to give 5 as a black solid Yield 60 mg

(94) 1H NMR (400 MHz THF-d8) δ 1148 (s 2H) 893 (d J = 46 Hz 2H) 879 (dd J = 46

21 Hz 4H) 873 (d J = 47 Hz 2H) 860 (d J = 47 Hz 2H) 836 (d J = 47 Hz 2H) 827ndash810

(m 12H) 797 (d J = 47 Hz 2H) 788ndash785 (m 6H) 776ndash758 (m 6H) 718ndash699 (m 12H)

675 (d J = 90 Hz 8H) 388 (t J = 63 Hz 8H) 150ndash136 (m 8H) 136ndash112 (m 40H)

090ndash076 (m 12H) 13C NMR (101 MHz THFndashd8) δ 16798 15711 15615 15603 15204

15116 15113 15103 15096 15022 14937 14923 14482 14184 13619 13612 13593

13561 13540 13473 13445 13265 13256 13238 13228 13173 13159 13096 12863

12834 12803 12740 12338 12228 12093 11843 11624 6889 3297 3051 3041 2723

S6

2370 1459 1458 HRMS (MALDI-TOF) mz [M+H]+ calcd for C134H129N10O8Zn2 21338572

found 21338523 FT-IR (KBr) νmax 3038 2926 2856 1731 1694 1603 1502 1237 1000 cm-1

Anal Calcd For C134H128N10O8Zn2 C 7530 H 604 N 655 Found C 7511 H 631 N 629

Synthesis of compound 5 Porphyrin 1 (400 mg 042 mmol) was dissolved in CH2Cl2MeOH

(vv = 91 150 mL) and NBS (150 mg 085 mmol) was added The reaction mixture was stirred

under air at room temperature for 15 min and quenched with acetone (10 mL) The solvent was

evaporated After evaporation of the solvent the product was isolated by column chromatography

(silica gel) using CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red

solid Yield 037 g (80) 1H NMR (400 MHz CDCl3) δ 962 (t J = 44 Hz 4H) 901 (d J = 45

Hz 2H) 875 (d J = 41 Hz 2H) 845 (d J = 81 Hz 2H) 824 (d J = 78 Hz 2H) 792 (d J =

84 Hz 2H) 737 (d J = 89 Hz 4H) 729 (d J = 85 Hz 2H) 699 (d J = 89 Hz 4H) 413 (s

3H) 401 (t J = 65 Hz 4H) 189ndash173 (m 4H) 152ndash144 (m 4H) 143ndash121 (m 16H)

097ndash079 (m 6H) -269 (s 2H) 13C NMR (101 MHz CDCl3) δ 16742 15624 14913 14645

14070 13580 13473 13262 13008 12825 12759 12293 11956 11782 11578 10412

6858 5270 3206 2963 2949 2635 2290 1433 HRMS (MALDI-TOF) mz [M+H]+ calcd

for C62H64Br2N5O4 11003320 found 11003335 FT-IR (KBr) νmax 3322 3038 2924 2855

1723 1602 1503 1278 1240 1108 cm-1

Synthesis of compound 6 A 100 mL round bottom flask containing porphyrin 5 (143 mg 013

mmol) phenylboronic acid (100 mg 082 mmol) Pd(PPh3)4 (18 mg 0016 mmol) and Cs2CO3

(251 mg 077 mmol) was evacuated and flushed with nitrogen three times TolueneDMF (vv =

51 60 mL) was added The reaction mixture was heated to 90 oC for 8 h with vigorous stirring

After addition of water and dichloromethane the organic phase was separated the aqueous layer

was extracted three times with CH2Cl2 and the combined organic layer was dried over MgSO4

and filtered Then Zn(OAc)22H2O (283 mg 129 mmol) in CH3OH (10 mL) was added the

mixture was stirred at room temperature for 05 h Then the solvent was removed under reduced

pressure After addition of water and dichloromethane the organic phase was separated the

aqueous layer was extracted three times with CH2Cl2 the combined organic layer was dried over

MgSO4 and filtered The product was isolated by column chromatography (silica gel) using

CH2Cl2 as eluent Recrystallization from CH2Cl2CH3OH gave a red solid Yield 115 mg (76) 1H NMR (400 MHz CDCl3) δ 912 (d J = 46 Hz 2H) 896 (t 4H) 887 (d J = 47 Hz 2H)

842 (d J = 82 Hz 2H) 830 (d J = 80 Hz 2H) 822 (d J = 64 Hz 4H) 799 (d J = 84 Hz

2H) 784ndash767 (m 6H) 735 (d J = 88 Hz 4H) 729 (d J = 84 Hz 2H) 695 (d J = 89 Hz

4H) 410 (s 3H) 398 (t J = 65 Hz 4H) 187ndash171 (m 4H) 152ndash142 (m 4H) 141ndash116 (m

16H) 089 (t J = 66 Hz 6H) 13C NMR (101 MHz CDCl3) δ 16764 15595 15094 15054

15030 14982 14858 14805 14299 14101 13546 13466 13435 13262 13249 13214

13161 12952 12799 12776 12733 12679 12237 12147 11948 11807 11569 6855

5259 3205 2962 2948 2634 2289 1433 HRMS (MALDI-TOF) mz [M]+ calcd for

C74H71N5O4Zn 11574792 found 11574798 FT-IR (KBr) νmax 3042 2926 2855 1725 1603

1502 1278 1237 1001 cm-1

Synthesis of compound JY06 A mixture of porphyrin 6 (127 mg 011 mmol) and KOH

(056 g 10 mmol) in THFEtOHH2O (1101 50 ml) was refluxed for 12 h The mixture was

S7

then cooled to room temperature acidified with 01 M HCl to PH = 5 50 mL CH2Cl2 was added

The solution was washed three times with water and the combined organic layer was dried with

MgSO4 and removed by vacuo The residue was purified by flash column chromatography (silica

gel CH2Cl2CH3OH=101) to give JY06 as a red solid Yield 110 mg (87) 1H NMR (400 MHz

THF) δ 1164 (s 1H) 901 (d J = 46 Hz 2H) 891ndash873 (m 6H) 842 (d J = 81 Hz 2H) 829

(d J = 81 Hz 2H) 826ndash811 (m 4H) 798 (d J = 85 Hz 2H) 786ndash764 (m 6H) 742ndash718 (m

6H) 696 (d J = 90 Hz 4H) 399 (t J = 64 Hz 4H) 188ndash174 (m 4H) 160ndash145 (m 4H)

144ndash121 (m 16H) 102ndash076 (m 6H) 13C NMR (101 MHz THF) δ 16807 15721 15164

15123 15104 15067 14949 14925 14473 14193 13633 13593 13555 13547 13274

13261 13222 13191 13104 12871 12827 12815 12734 12256 12171 12008 11851

11635 6898 3300 3056 3054 3044 2728 2373 1460 HRMS (MALDI-TOF) mz [M]+

calcd for C73H69N5O4Zn 11434636 found 11434638 FT-IR (KBr) νmax 3041 2925 2854 1734

1693 1604 1502 1237 1001 cm-1 Anal Calcd For C73H69N5O4Zn C 7653 H 607 N 611

Found C 7639 H 602 N 609

S8

Fig S1 Fluorescence spectra of JY06 and JY07 in THF

Fig S2 Frontier orbitals of JY06 and JY07 (HOMO and LUMO)

Fig S3 FTIR spectra of (a) JY06 and (b) JY07 powders and stained TiO2 films

Fig S4 The photocurrent density-voltage (J-V) curves based on JY07 with and without CDCA

S9

Table S1 Photovoltaic performance for DSSCs based on JY07

dye CDCA (mM) Voc (V) Jsc (mAcm2) FF η () Γ (nmol cm-2)

JY07 0 065 1320 062 533 62

JY07 10 065 1220 061 485 45 aActive area 016 cm2 Electrolyte is composed of 03 M 12-dimethyl-3-propylimidazolium iodide (DMPII) 01

M LiI 005 M I2 and 05 M 4-tert -butyl pyridine in acetonitrile

Photostability study The long-term stability of DSSCs is a critical requirement for their photovoltaic application We

have used a straightforward method reported in literature to examine the stability of studied dyes5 For the stability study TiO2 thin films with areas of 1times1 cm2 and thicknesses of 3-4 μm were used

The films were immersed in a 03 mM solution of the porphyrin in THF for 05 h dried and the

absorbance was measured Then the same films were irradiated under standard one-sun

illumination for 5 min and 30 min and the absorbance was measured again

Fig S5 Absorption spectra of (a) JY06 and (b) JY07 that were adsorbed onto TiO2 films after

irradiation for 0 5 and 30 min

Fig S6 EIS spectra of DSSCs tested at -06 V forward bias in the dark (a) Nyquist and (b) Bode

phase plots

S10

References (1) J-W Ka and C-H Lee Tetrahedron Lett 2000 41 4609

(2) M Yoshida T Doi S Kang J Watanabe and T Takahashi Chem Commun 2009 2756

(3) J Mao N He Z Ning Q Zhang F Guo L Chen W Wu J Hua and H Tian Angew Chem

Int Ed 2012 51 9873

(4) Y Y Dou G R Li J Song and X P Gao Phys Chem Chem Phys 2012 14 1339

(5) (a) R B Ambre G-F Chang and C-H Hung Chem Commun 2014 50 725 (b) Y Wu M

Marszalek S M Zakeeruddin Q Zhang H Tian M Graumltzel and W Zhu Energy Environ

Sci 2012 5 8261 (c) R Katoh A Furube S Mori M Miyashita K Sunahara N Koumura

and K Hara Energy Environ Sci 2009 2 542

S11

1H NMR and 13C NMR spectra

Fig S7 1H NMR spectrum of compound 1 in CDCl3

Fig S8 13C NMR spectrum of compound 1 in CDCl3

S12

Fig S9 1H NMR spectrum of compound 2 in CDCl3

Fig S10 13C NMR spectrum of compound 2 in CDCl3

S13

Fig S11 1H NMR spectrum of compound 3 in CDCl3

Fig S12 13C NMR spectrum of compound 3 in CDCl3

S14

Fig S13 1H NMR spectrum of compound 4 in CDCl3

Fig S14 13C NMR spectrum of compound 4 in CDCl3

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 4: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S4

Scheme S1 Syntheses of JY06 and JY07

Synthesis of compound 1 To a degassed solution of dipyrromethane (731 mg 5 mmol)

4-(bis(4-(octyloxy)phenyl)amino)benzaldehyde (132 g 25 mmol) and methyl 4-formylbenzoate

(4105 mg 25 mmol) in CH2Cl2 (500 mL) was added CF3COOH (022 mL 3 mmol) The mixture

was stirred in the dark for 10 h and then DDQ (10 g 45mmol) was added After another 1 h

Et3N (50 mL) was added and the solvent was removed under reduced pressure Purification by

silica gel column chromatography (CH2Cl2PE = 31) and recrystallization from CH2Cl2MeOH

afforded compound 1 as a purple red solid Yield 460 mg (19) 1H NMR (400 MHz CDCl3) δ

1032 (s 2H) 941 (t J = 47 Hz 4H) 925 (d J = 46 Hz 2H) 902 (d J = 46 Hz 2H) 849 (d J

= 80 Hz 2H) 836 (d J = 80 Hz 2H) 806 (d J = 83 Hz 2H) 745ndash730 (m 6H) 699 (d J =

88 Hz 4H) 414 (s 3H) 401 (t J = 65 Hz 4H) 189ndash177 (m 4H) 155ndash145 (m 4H)

143ndash125 (m 16H) 098ndash086 (m 6H) ndash305 (s 2H) 13C NMR (101 MHz CDCl3) δ 16764

15607 14884 14786 14688 14657 14541 14526 14090 13598 13509 13280 13215

13173 13164 13063 12966 12839 12743 12047 11845 11731 11572 10562 6856

5267 3206 2963 2949 2635 2290 1434 HRMS (MALDI-TOF) mz [M+H]+ calcd for

C62H66N5O4 9445109 found 9445108 FT-IR (KBr) νmax 3271 3038 2925 2854 1719 1603

1504 1278 1240 1108 cm-1

Synthesis of compound 2 Porphyrin 1 (943 mg 10 mmol) was dissolved in CH2Cl2MeOH

(vv = 91 200 mL) and NBS (196 mg 11 mmol) was added The reaction mixture was stirred

under air at room temperature for 15 min and quenched with acetone (10 mL) The solvent was

evaporated After evaporation of the solvent the product was isolated by column chromatography

(silica gel) using CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red

solid Yield 562 mg (55) 1H NMR (400 MHz CDCl3) δ 1016 (s 1H) 974 (t J = 43 Hz 2H)

929 (t J = 54 Hz 2H) 912 (t J = 51 Hz 2H) 887 (t J = 40 Hz 2H) 847 (d J = 80 Hz 2H)

829 (d J = 80 Hz 2H) 798 (d J = 83 Hz 2H) 737 (d J = 88 Hz 4H) 732 (d J = 83 Hz

2H) 698 (d J = 88 Hz 4H) 413 (s 3H) 400 (t J = 65 Hz 4H) 189ndash174 (m 4H) 154ndash144

(m 4H) 143ndash120 (m 16H) 089 (t J = 66 Hz 6H) ndash297 (s 2H) 13C NMR (101 MHz CDCl3)

δ 16732 15594 14877 14629 14058 13568 13469 13248 12967 12811 12731 12150

11824 11790 11553 10571 10379 6835 5249 3186 2943 2942 2929 2614 2270

1414 HRMS (MALDI-TOF) mz [M+H]+ calcd for C62H65BrN5O4 10224214 found

10224216 FT-IR (KBr) νmax 3301 3038 2925 2855 1718 1603 1504 1279 1239 1109 cm-1

Synthesis of compound 3 A 100 mL round bottom flask containing porphyrin 2 (133 mg

013 mmol) phenylboronic acid (50 mg 041 mmol) Pd(PPh3)4 (18 mg 0016 mmol) and Cs2CO3

(251 mg 077 mmol) was evacuated and flushed with nitrogen three times TolueneDMF (vv =

51 60 mL) was added The reaction mixture was heated to 90 oC for 8 h with vigorous stirring

After addition of water and dichloromethane the organic phase was separated the aqueous layer

was extracted three times with CH2Cl2 and the combined organic layer was dried over MgSO4

and filtered Then Zn(OAc)22H2O (283 mg 129 mmol) in CH3OH (10 mL) was added the

mixture was stirred at room temperature for 05 h Then the solvent was removed under reduced

pressure After addition of water and dichloromethane the organic phase was separated the

aqueous layer was extracted three times with CH2Cl2 the combined organic layer was dried over

S5

MgSO4 and filtered The product was isolated by column chromatography (silica gel) using

CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red solid Yield 118 mg

(84) 1H NMR (400 MHz CDCl3) δ 1022 (s 1H) 939 (dd J = 91 45 Hz 2H) 926 (d J =

45 Hz 1H) 916 (d J = 46 Hz 1H) 908ndash894 (m 3H) 891 (d J = 46 Hz 1H) 843 (d J = 81

Hz 2H) 831 (d J = 80 Hz 2H) 822 (d J = 63 Hz 2H) 801 (d J = 84 Hz 2H) 785ndash768 (m

3H) 737 (d J = 89 Hz 4H) 731 (d J = 84 Hz 2H) 696 (d J = 89 Hz 4H) 410 (s 3H) 399

(t J = 65 Hz 4H) 189ndash173 (m 4H) 149ndash143 (m 4H) 141ndash119 (m 16H) 099ndash078 (m 6H) 13C NMR (101 MHz CDCl3) δ 16743 15570 15064 15062 14989 14971 14970 14965

14951 14835 14770 14286 14080 13534 13454 13444 13401 13300 13227 13198

13194 13163 13126 12922 12779 12753 12710 12652 12160 12156 11871 11795

11546 10594 6832 5238 3184 2940 2938 2927 2611 2268 1412 HRMS

(MALDI-TOF) mz [M+H]+ calcd for C68H68N5O4Zn 10824557 found 10824535 FT-IR (KBr)

νmax 3035 2925 2854 1723 1603 1502 1276 1238 997 cm-1

Synthesis of compound 4 To a degassed solution of porphyrin 3 (271 mg 025 mmol) in

CH2Cl2 (100 ml) was added PIFA (55 mg 013 mmol) The mixture was stirred at room

temperature for 1 min The resulting yellow-brown mixture was then washed with water dried

with anhydrous Na2SO4 filtered and concentrated in vacuo The residue was purified by flash

column chromatography (silica gel CH2Cl2) to give 4 as a black solid Yield 219 mg (82) 1H

NMR (400 MHz CDCl3) δ 917 (d J = 47 Hz 2H) 903 (t J = 48 Hz 4H) 891 (d J = 47 Hz

2H) 883 (d J = 47 Hz 2H) 858 (d J = 47 Hz 2H) 836ndash823 (m 12H) 817ndash807 (m 4H)

804ndash793 (m 4H) 788ndash775 (m 6H) 725ndash715 (m 12H) 685 (d J = 89 Hz 8H) 394 (s 6H)

390 (t J = 65 Hz 8H) 181ndash167 (m 8H) 147ndash137 (m 8H) 133ndash119 (m 32H) 090ndash081 (m

12H) 13C NMR (101 MHz CDCl3) δ 16729 15562 15501 15480 15121 15032 15026

15006 15003 14923 14827 14772 14285 14070 13518 13511 13450 13440 13414

13404 13388 13242 13234 13228 13210 13140 13128 12916 12769 12764 12699

12665 12295 12201 12008 11959 11784 11537 6826 5226 3181 2936 2934 2923

2607 2265 1410 HRMS (MALDI-TOF) mz [M+H]+ calcd for C136H133N10O8Zn2 21618885

found 21618862 FT-IR (KBr) νmax 3037 2925 2854 1725 1604 1503 1320 1271 1000 cm-1

Synthesis of compound JY07 A mixture of porphyrin 4 (65 mg 003 mmol) and KOH (056

g 10 mmol) in THFEtOHH2O (1101 50 ml) was refluxed for 12 h The mixture was then

cooled to room temperature acidified with 01 M HCl to PH = 5 50 mL CH2Cl2 was added The

organic phase was separated the aqueous layer was extracted three times with CH2Cl2 and the

combined organic layer was dried over MgSO4 and filtered The residue was purified by flash

column chromatography (silica gel CH2Cl2CH3OH=51) to give 5 as a black solid Yield 60 mg

(94) 1H NMR (400 MHz THF-d8) δ 1148 (s 2H) 893 (d J = 46 Hz 2H) 879 (dd J = 46

21 Hz 4H) 873 (d J = 47 Hz 2H) 860 (d J = 47 Hz 2H) 836 (d J = 47 Hz 2H) 827ndash810

(m 12H) 797 (d J = 47 Hz 2H) 788ndash785 (m 6H) 776ndash758 (m 6H) 718ndash699 (m 12H)

675 (d J = 90 Hz 8H) 388 (t J = 63 Hz 8H) 150ndash136 (m 8H) 136ndash112 (m 40H)

090ndash076 (m 12H) 13C NMR (101 MHz THFndashd8) δ 16798 15711 15615 15603 15204

15116 15113 15103 15096 15022 14937 14923 14482 14184 13619 13612 13593

13561 13540 13473 13445 13265 13256 13238 13228 13173 13159 13096 12863

12834 12803 12740 12338 12228 12093 11843 11624 6889 3297 3051 3041 2723

S6

2370 1459 1458 HRMS (MALDI-TOF) mz [M+H]+ calcd for C134H129N10O8Zn2 21338572

found 21338523 FT-IR (KBr) νmax 3038 2926 2856 1731 1694 1603 1502 1237 1000 cm-1

Anal Calcd For C134H128N10O8Zn2 C 7530 H 604 N 655 Found C 7511 H 631 N 629

Synthesis of compound 5 Porphyrin 1 (400 mg 042 mmol) was dissolved in CH2Cl2MeOH

(vv = 91 150 mL) and NBS (150 mg 085 mmol) was added The reaction mixture was stirred

under air at room temperature for 15 min and quenched with acetone (10 mL) The solvent was

evaporated After evaporation of the solvent the product was isolated by column chromatography

(silica gel) using CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red

solid Yield 037 g (80) 1H NMR (400 MHz CDCl3) δ 962 (t J = 44 Hz 4H) 901 (d J = 45

Hz 2H) 875 (d J = 41 Hz 2H) 845 (d J = 81 Hz 2H) 824 (d J = 78 Hz 2H) 792 (d J =

84 Hz 2H) 737 (d J = 89 Hz 4H) 729 (d J = 85 Hz 2H) 699 (d J = 89 Hz 4H) 413 (s

3H) 401 (t J = 65 Hz 4H) 189ndash173 (m 4H) 152ndash144 (m 4H) 143ndash121 (m 16H)

097ndash079 (m 6H) -269 (s 2H) 13C NMR (101 MHz CDCl3) δ 16742 15624 14913 14645

14070 13580 13473 13262 13008 12825 12759 12293 11956 11782 11578 10412

6858 5270 3206 2963 2949 2635 2290 1433 HRMS (MALDI-TOF) mz [M+H]+ calcd

for C62H64Br2N5O4 11003320 found 11003335 FT-IR (KBr) νmax 3322 3038 2924 2855

1723 1602 1503 1278 1240 1108 cm-1

Synthesis of compound 6 A 100 mL round bottom flask containing porphyrin 5 (143 mg 013

mmol) phenylboronic acid (100 mg 082 mmol) Pd(PPh3)4 (18 mg 0016 mmol) and Cs2CO3

(251 mg 077 mmol) was evacuated and flushed with nitrogen three times TolueneDMF (vv =

51 60 mL) was added The reaction mixture was heated to 90 oC for 8 h with vigorous stirring

After addition of water and dichloromethane the organic phase was separated the aqueous layer

was extracted three times with CH2Cl2 and the combined organic layer was dried over MgSO4

and filtered Then Zn(OAc)22H2O (283 mg 129 mmol) in CH3OH (10 mL) was added the

mixture was stirred at room temperature for 05 h Then the solvent was removed under reduced

pressure After addition of water and dichloromethane the organic phase was separated the

aqueous layer was extracted three times with CH2Cl2 the combined organic layer was dried over

MgSO4 and filtered The product was isolated by column chromatography (silica gel) using

CH2Cl2 as eluent Recrystallization from CH2Cl2CH3OH gave a red solid Yield 115 mg (76) 1H NMR (400 MHz CDCl3) δ 912 (d J = 46 Hz 2H) 896 (t 4H) 887 (d J = 47 Hz 2H)

842 (d J = 82 Hz 2H) 830 (d J = 80 Hz 2H) 822 (d J = 64 Hz 4H) 799 (d J = 84 Hz

2H) 784ndash767 (m 6H) 735 (d J = 88 Hz 4H) 729 (d J = 84 Hz 2H) 695 (d J = 89 Hz

4H) 410 (s 3H) 398 (t J = 65 Hz 4H) 187ndash171 (m 4H) 152ndash142 (m 4H) 141ndash116 (m

16H) 089 (t J = 66 Hz 6H) 13C NMR (101 MHz CDCl3) δ 16764 15595 15094 15054

15030 14982 14858 14805 14299 14101 13546 13466 13435 13262 13249 13214

13161 12952 12799 12776 12733 12679 12237 12147 11948 11807 11569 6855

5259 3205 2962 2948 2634 2289 1433 HRMS (MALDI-TOF) mz [M]+ calcd for

C74H71N5O4Zn 11574792 found 11574798 FT-IR (KBr) νmax 3042 2926 2855 1725 1603

1502 1278 1237 1001 cm-1

Synthesis of compound JY06 A mixture of porphyrin 6 (127 mg 011 mmol) and KOH

(056 g 10 mmol) in THFEtOHH2O (1101 50 ml) was refluxed for 12 h The mixture was

S7

then cooled to room temperature acidified with 01 M HCl to PH = 5 50 mL CH2Cl2 was added

The solution was washed three times with water and the combined organic layer was dried with

MgSO4 and removed by vacuo The residue was purified by flash column chromatography (silica

gel CH2Cl2CH3OH=101) to give JY06 as a red solid Yield 110 mg (87) 1H NMR (400 MHz

THF) δ 1164 (s 1H) 901 (d J = 46 Hz 2H) 891ndash873 (m 6H) 842 (d J = 81 Hz 2H) 829

(d J = 81 Hz 2H) 826ndash811 (m 4H) 798 (d J = 85 Hz 2H) 786ndash764 (m 6H) 742ndash718 (m

6H) 696 (d J = 90 Hz 4H) 399 (t J = 64 Hz 4H) 188ndash174 (m 4H) 160ndash145 (m 4H)

144ndash121 (m 16H) 102ndash076 (m 6H) 13C NMR (101 MHz THF) δ 16807 15721 15164

15123 15104 15067 14949 14925 14473 14193 13633 13593 13555 13547 13274

13261 13222 13191 13104 12871 12827 12815 12734 12256 12171 12008 11851

11635 6898 3300 3056 3054 3044 2728 2373 1460 HRMS (MALDI-TOF) mz [M]+

calcd for C73H69N5O4Zn 11434636 found 11434638 FT-IR (KBr) νmax 3041 2925 2854 1734

1693 1604 1502 1237 1001 cm-1 Anal Calcd For C73H69N5O4Zn C 7653 H 607 N 611

Found C 7639 H 602 N 609

S8

Fig S1 Fluorescence spectra of JY06 and JY07 in THF

Fig S2 Frontier orbitals of JY06 and JY07 (HOMO and LUMO)

Fig S3 FTIR spectra of (a) JY06 and (b) JY07 powders and stained TiO2 films

Fig S4 The photocurrent density-voltage (J-V) curves based on JY07 with and without CDCA

S9

Table S1 Photovoltaic performance for DSSCs based on JY07

dye CDCA (mM) Voc (V) Jsc (mAcm2) FF η () Γ (nmol cm-2)

JY07 0 065 1320 062 533 62

JY07 10 065 1220 061 485 45 aActive area 016 cm2 Electrolyte is composed of 03 M 12-dimethyl-3-propylimidazolium iodide (DMPII) 01

M LiI 005 M I2 and 05 M 4-tert -butyl pyridine in acetonitrile

Photostability study The long-term stability of DSSCs is a critical requirement for their photovoltaic application We

have used a straightforward method reported in literature to examine the stability of studied dyes5 For the stability study TiO2 thin films with areas of 1times1 cm2 and thicknesses of 3-4 μm were used

The films were immersed in a 03 mM solution of the porphyrin in THF for 05 h dried and the

absorbance was measured Then the same films were irradiated under standard one-sun

illumination for 5 min and 30 min and the absorbance was measured again

Fig S5 Absorption spectra of (a) JY06 and (b) JY07 that were adsorbed onto TiO2 films after

irradiation for 0 5 and 30 min

Fig S6 EIS spectra of DSSCs tested at -06 V forward bias in the dark (a) Nyquist and (b) Bode

phase plots

S10

References (1) J-W Ka and C-H Lee Tetrahedron Lett 2000 41 4609

(2) M Yoshida T Doi S Kang J Watanabe and T Takahashi Chem Commun 2009 2756

(3) J Mao N He Z Ning Q Zhang F Guo L Chen W Wu J Hua and H Tian Angew Chem

Int Ed 2012 51 9873

(4) Y Y Dou G R Li J Song and X P Gao Phys Chem Chem Phys 2012 14 1339

(5) (a) R B Ambre G-F Chang and C-H Hung Chem Commun 2014 50 725 (b) Y Wu M

Marszalek S M Zakeeruddin Q Zhang H Tian M Graumltzel and W Zhu Energy Environ

Sci 2012 5 8261 (c) R Katoh A Furube S Mori M Miyashita K Sunahara N Koumura

and K Hara Energy Environ Sci 2009 2 542

S11

1H NMR and 13C NMR spectra

Fig S7 1H NMR spectrum of compound 1 in CDCl3

Fig S8 13C NMR spectrum of compound 1 in CDCl3

S12

Fig S9 1H NMR spectrum of compound 2 in CDCl3

Fig S10 13C NMR spectrum of compound 2 in CDCl3

S13

Fig S11 1H NMR spectrum of compound 3 in CDCl3

Fig S12 13C NMR spectrum of compound 3 in CDCl3

S14

Fig S13 1H NMR spectrum of compound 4 in CDCl3

Fig S14 13C NMR spectrum of compound 4 in CDCl3

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 5: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S5

MgSO4 and filtered The product was isolated by column chromatography (silica gel) using

CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red solid Yield 118 mg

(84) 1H NMR (400 MHz CDCl3) δ 1022 (s 1H) 939 (dd J = 91 45 Hz 2H) 926 (d J =

45 Hz 1H) 916 (d J = 46 Hz 1H) 908ndash894 (m 3H) 891 (d J = 46 Hz 1H) 843 (d J = 81

Hz 2H) 831 (d J = 80 Hz 2H) 822 (d J = 63 Hz 2H) 801 (d J = 84 Hz 2H) 785ndash768 (m

3H) 737 (d J = 89 Hz 4H) 731 (d J = 84 Hz 2H) 696 (d J = 89 Hz 4H) 410 (s 3H) 399

(t J = 65 Hz 4H) 189ndash173 (m 4H) 149ndash143 (m 4H) 141ndash119 (m 16H) 099ndash078 (m 6H) 13C NMR (101 MHz CDCl3) δ 16743 15570 15064 15062 14989 14971 14970 14965

14951 14835 14770 14286 14080 13534 13454 13444 13401 13300 13227 13198

13194 13163 13126 12922 12779 12753 12710 12652 12160 12156 11871 11795

11546 10594 6832 5238 3184 2940 2938 2927 2611 2268 1412 HRMS

(MALDI-TOF) mz [M+H]+ calcd for C68H68N5O4Zn 10824557 found 10824535 FT-IR (KBr)

νmax 3035 2925 2854 1723 1603 1502 1276 1238 997 cm-1

Synthesis of compound 4 To a degassed solution of porphyrin 3 (271 mg 025 mmol) in

CH2Cl2 (100 ml) was added PIFA (55 mg 013 mmol) The mixture was stirred at room

temperature for 1 min The resulting yellow-brown mixture was then washed with water dried

with anhydrous Na2SO4 filtered and concentrated in vacuo The residue was purified by flash

column chromatography (silica gel CH2Cl2) to give 4 as a black solid Yield 219 mg (82) 1H

NMR (400 MHz CDCl3) δ 917 (d J = 47 Hz 2H) 903 (t J = 48 Hz 4H) 891 (d J = 47 Hz

2H) 883 (d J = 47 Hz 2H) 858 (d J = 47 Hz 2H) 836ndash823 (m 12H) 817ndash807 (m 4H)

804ndash793 (m 4H) 788ndash775 (m 6H) 725ndash715 (m 12H) 685 (d J = 89 Hz 8H) 394 (s 6H)

390 (t J = 65 Hz 8H) 181ndash167 (m 8H) 147ndash137 (m 8H) 133ndash119 (m 32H) 090ndash081 (m

12H) 13C NMR (101 MHz CDCl3) δ 16729 15562 15501 15480 15121 15032 15026

15006 15003 14923 14827 14772 14285 14070 13518 13511 13450 13440 13414

13404 13388 13242 13234 13228 13210 13140 13128 12916 12769 12764 12699

12665 12295 12201 12008 11959 11784 11537 6826 5226 3181 2936 2934 2923

2607 2265 1410 HRMS (MALDI-TOF) mz [M+H]+ calcd for C136H133N10O8Zn2 21618885

found 21618862 FT-IR (KBr) νmax 3037 2925 2854 1725 1604 1503 1320 1271 1000 cm-1

Synthesis of compound JY07 A mixture of porphyrin 4 (65 mg 003 mmol) and KOH (056

g 10 mmol) in THFEtOHH2O (1101 50 ml) was refluxed for 12 h The mixture was then

cooled to room temperature acidified with 01 M HCl to PH = 5 50 mL CH2Cl2 was added The

organic phase was separated the aqueous layer was extracted three times with CH2Cl2 and the

combined organic layer was dried over MgSO4 and filtered The residue was purified by flash

column chromatography (silica gel CH2Cl2CH3OH=51) to give 5 as a black solid Yield 60 mg

(94) 1H NMR (400 MHz THF-d8) δ 1148 (s 2H) 893 (d J = 46 Hz 2H) 879 (dd J = 46

21 Hz 4H) 873 (d J = 47 Hz 2H) 860 (d J = 47 Hz 2H) 836 (d J = 47 Hz 2H) 827ndash810

(m 12H) 797 (d J = 47 Hz 2H) 788ndash785 (m 6H) 776ndash758 (m 6H) 718ndash699 (m 12H)

675 (d J = 90 Hz 8H) 388 (t J = 63 Hz 8H) 150ndash136 (m 8H) 136ndash112 (m 40H)

090ndash076 (m 12H) 13C NMR (101 MHz THFndashd8) δ 16798 15711 15615 15603 15204

15116 15113 15103 15096 15022 14937 14923 14482 14184 13619 13612 13593

13561 13540 13473 13445 13265 13256 13238 13228 13173 13159 13096 12863

12834 12803 12740 12338 12228 12093 11843 11624 6889 3297 3051 3041 2723

S6

2370 1459 1458 HRMS (MALDI-TOF) mz [M+H]+ calcd for C134H129N10O8Zn2 21338572

found 21338523 FT-IR (KBr) νmax 3038 2926 2856 1731 1694 1603 1502 1237 1000 cm-1

Anal Calcd For C134H128N10O8Zn2 C 7530 H 604 N 655 Found C 7511 H 631 N 629

Synthesis of compound 5 Porphyrin 1 (400 mg 042 mmol) was dissolved in CH2Cl2MeOH

(vv = 91 150 mL) and NBS (150 mg 085 mmol) was added The reaction mixture was stirred

under air at room temperature for 15 min and quenched with acetone (10 mL) The solvent was

evaporated After evaporation of the solvent the product was isolated by column chromatography

(silica gel) using CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red

solid Yield 037 g (80) 1H NMR (400 MHz CDCl3) δ 962 (t J = 44 Hz 4H) 901 (d J = 45

Hz 2H) 875 (d J = 41 Hz 2H) 845 (d J = 81 Hz 2H) 824 (d J = 78 Hz 2H) 792 (d J =

84 Hz 2H) 737 (d J = 89 Hz 4H) 729 (d J = 85 Hz 2H) 699 (d J = 89 Hz 4H) 413 (s

3H) 401 (t J = 65 Hz 4H) 189ndash173 (m 4H) 152ndash144 (m 4H) 143ndash121 (m 16H)

097ndash079 (m 6H) -269 (s 2H) 13C NMR (101 MHz CDCl3) δ 16742 15624 14913 14645

14070 13580 13473 13262 13008 12825 12759 12293 11956 11782 11578 10412

6858 5270 3206 2963 2949 2635 2290 1433 HRMS (MALDI-TOF) mz [M+H]+ calcd

for C62H64Br2N5O4 11003320 found 11003335 FT-IR (KBr) νmax 3322 3038 2924 2855

1723 1602 1503 1278 1240 1108 cm-1

Synthesis of compound 6 A 100 mL round bottom flask containing porphyrin 5 (143 mg 013

mmol) phenylboronic acid (100 mg 082 mmol) Pd(PPh3)4 (18 mg 0016 mmol) and Cs2CO3

(251 mg 077 mmol) was evacuated and flushed with nitrogen three times TolueneDMF (vv =

51 60 mL) was added The reaction mixture was heated to 90 oC for 8 h with vigorous stirring

After addition of water and dichloromethane the organic phase was separated the aqueous layer

was extracted three times with CH2Cl2 and the combined organic layer was dried over MgSO4

and filtered Then Zn(OAc)22H2O (283 mg 129 mmol) in CH3OH (10 mL) was added the

mixture was stirred at room temperature for 05 h Then the solvent was removed under reduced

pressure After addition of water and dichloromethane the organic phase was separated the

aqueous layer was extracted three times with CH2Cl2 the combined organic layer was dried over

MgSO4 and filtered The product was isolated by column chromatography (silica gel) using

CH2Cl2 as eluent Recrystallization from CH2Cl2CH3OH gave a red solid Yield 115 mg (76) 1H NMR (400 MHz CDCl3) δ 912 (d J = 46 Hz 2H) 896 (t 4H) 887 (d J = 47 Hz 2H)

842 (d J = 82 Hz 2H) 830 (d J = 80 Hz 2H) 822 (d J = 64 Hz 4H) 799 (d J = 84 Hz

2H) 784ndash767 (m 6H) 735 (d J = 88 Hz 4H) 729 (d J = 84 Hz 2H) 695 (d J = 89 Hz

4H) 410 (s 3H) 398 (t J = 65 Hz 4H) 187ndash171 (m 4H) 152ndash142 (m 4H) 141ndash116 (m

16H) 089 (t J = 66 Hz 6H) 13C NMR (101 MHz CDCl3) δ 16764 15595 15094 15054

15030 14982 14858 14805 14299 14101 13546 13466 13435 13262 13249 13214

13161 12952 12799 12776 12733 12679 12237 12147 11948 11807 11569 6855

5259 3205 2962 2948 2634 2289 1433 HRMS (MALDI-TOF) mz [M]+ calcd for

C74H71N5O4Zn 11574792 found 11574798 FT-IR (KBr) νmax 3042 2926 2855 1725 1603

1502 1278 1237 1001 cm-1

Synthesis of compound JY06 A mixture of porphyrin 6 (127 mg 011 mmol) and KOH

(056 g 10 mmol) in THFEtOHH2O (1101 50 ml) was refluxed for 12 h The mixture was

S7

then cooled to room temperature acidified with 01 M HCl to PH = 5 50 mL CH2Cl2 was added

The solution was washed three times with water and the combined organic layer was dried with

MgSO4 and removed by vacuo The residue was purified by flash column chromatography (silica

gel CH2Cl2CH3OH=101) to give JY06 as a red solid Yield 110 mg (87) 1H NMR (400 MHz

THF) δ 1164 (s 1H) 901 (d J = 46 Hz 2H) 891ndash873 (m 6H) 842 (d J = 81 Hz 2H) 829

(d J = 81 Hz 2H) 826ndash811 (m 4H) 798 (d J = 85 Hz 2H) 786ndash764 (m 6H) 742ndash718 (m

6H) 696 (d J = 90 Hz 4H) 399 (t J = 64 Hz 4H) 188ndash174 (m 4H) 160ndash145 (m 4H)

144ndash121 (m 16H) 102ndash076 (m 6H) 13C NMR (101 MHz THF) δ 16807 15721 15164

15123 15104 15067 14949 14925 14473 14193 13633 13593 13555 13547 13274

13261 13222 13191 13104 12871 12827 12815 12734 12256 12171 12008 11851

11635 6898 3300 3056 3054 3044 2728 2373 1460 HRMS (MALDI-TOF) mz [M]+

calcd for C73H69N5O4Zn 11434636 found 11434638 FT-IR (KBr) νmax 3041 2925 2854 1734

1693 1604 1502 1237 1001 cm-1 Anal Calcd For C73H69N5O4Zn C 7653 H 607 N 611

Found C 7639 H 602 N 609

S8

Fig S1 Fluorescence spectra of JY06 and JY07 in THF

Fig S2 Frontier orbitals of JY06 and JY07 (HOMO and LUMO)

Fig S3 FTIR spectra of (a) JY06 and (b) JY07 powders and stained TiO2 films

Fig S4 The photocurrent density-voltage (J-V) curves based on JY07 with and without CDCA

S9

Table S1 Photovoltaic performance for DSSCs based on JY07

dye CDCA (mM) Voc (V) Jsc (mAcm2) FF η () Γ (nmol cm-2)

JY07 0 065 1320 062 533 62

JY07 10 065 1220 061 485 45 aActive area 016 cm2 Electrolyte is composed of 03 M 12-dimethyl-3-propylimidazolium iodide (DMPII) 01

M LiI 005 M I2 and 05 M 4-tert -butyl pyridine in acetonitrile

Photostability study The long-term stability of DSSCs is a critical requirement for their photovoltaic application We

have used a straightforward method reported in literature to examine the stability of studied dyes5 For the stability study TiO2 thin films with areas of 1times1 cm2 and thicknesses of 3-4 μm were used

The films were immersed in a 03 mM solution of the porphyrin in THF for 05 h dried and the

absorbance was measured Then the same films were irradiated under standard one-sun

illumination for 5 min and 30 min and the absorbance was measured again

Fig S5 Absorption spectra of (a) JY06 and (b) JY07 that were adsorbed onto TiO2 films after

irradiation for 0 5 and 30 min

Fig S6 EIS spectra of DSSCs tested at -06 V forward bias in the dark (a) Nyquist and (b) Bode

phase plots

S10

References (1) J-W Ka and C-H Lee Tetrahedron Lett 2000 41 4609

(2) M Yoshida T Doi S Kang J Watanabe and T Takahashi Chem Commun 2009 2756

(3) J Mao N He Z Ning Q Zhang F Guo L Chen W Wu J Hua and H Tian Angew Chem

Int Ed 2012 51 9873

(4) Y Y Dou G R Li J Song and X P Gao Phys Chem Chem Phys 2012 14 1339

(5) (a) R B Ambre G-F Chang and C-H Hung Chem Commun 2014 50 725 (b) Y Wu M

Marszalek S M Zakeeruddin Q Zhang H Tian M Graumltzel and W Zhu Energy Environ

Sci 2012 5 8261 (c) R Katoh A Furube S Mori M Miyashita K Sunahara N Koumura

and K Hara Energy Environ Sci 2009 2 542

S11

1H NMR and 13C NMR spectra

Fig S7 1H NMR spectrum of compound 1 in CDCl3

Fig S8 13C NMR spectrum of compound 1 in CDCl3

S12

Fig S9 1H NMR spectrum of compound 2 in CDCl3

Fig S10 13C NMR spectrum of compound 2 in CDCl3

S13

Fig S11 1H NMR spectrum of compound 3 in CDCl3

Fig S12 13C NMR spectrum of compound 3 in CDCl3

S14

Fig S13 1H NMR spectrum of compound 4 in CDCl3

Fig S14 13C NMR spectrum of compound 4 in CDCl3

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 6: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S6

2370 1459 1458 HRMS (MALDI-TOF) mz [M+H]+ calcd for C134H129N10O8Zn2 21338572

found 21338523 FT-IR (KBr) νmax 3038 2926 2856 1731 1694 1603 1502 1237 1000 cm-1

Anal Calcd For C134H128N10O8Zn2 C 7530 H 604 N 655 Found C 7511 H 631 N 629

Synthesis of compound 5 Porphyrin 1 (400 mg 042 mmol) was dissolved in CH2Cl2MeOH

(vv = 91 150 mL) and NBS (150 mg 085 mmol) was added The reaction mixture was stirred

under air at room temperature for 15 min and quenched with acetone (10 mL) The solvent was

evaporated After evaporation of the solvent the product was isolated by column chromatography

(silica gel) using CH2Cl2PE = 31 as eluent Recrystallization from CH2Cl2CH3OH gave a red

solid Yield 037 g (80) 1H NMR (400 MHz CDCl3) δ 962 (t J = 44 Hz 4H) 901 (d J = 45

Hz 2H) 875 (d J = 41 Hz 2H) 845 (d J = 81 Hz 2H) 824 (d J = 78 Hz 2H) 792 (d J =

84 Hz 2H) 737 (d J = 89 Hz 4H) 729 (d J = 85 Hz 2H) 699 (d J = 89 Hz 4H) 413 (s

3H) 401 (t J = 65 Hz 4H) 189ndash173 (m 4H) 152ndash144 (m 4H) 143ndash121 (m 16H)

097ndash079 (m 6H) -269 (s 2H) 13C NMR (101 MHz CDCl3) δ 16742 15624 14913 14645

14070 13580 13473 13262 13008 12825 12759 12293 11956 11782 11578 10412

6858 5270 3206 2963 2949 2635 2290 1433 HRMS (MALDI-TOF) mz [M+H]+ calcd

for C62H64Br2N5O4 11003320 found 11003335 FT-IR (KBr) νmax 3322 3038 2924 2855

1723 1602 1503 1278 1240 1108 cm-1

Synthesis of compound 6 A 100 mL round bottom flask containing porphyrin 5 (143 mg 013

mmol) phenylboronic acid (100 mg 082 mmol) Pd(PPh3)4 (18 mg 0016 mmol) and Cs2CO3

(251 mg 077 mmol) was evacuated and flushed with nitrogen three times TolueneDMF (vv =

51 60 mL) was added The reaction mixture was heated to 90 oC for 8 h with vigorous stirring

After addition of water and dichloromethane the organic phase was separated the aqueous layer

was extracted three times with CH2Cl2 and the combined organic layer was dried over MgSO4

and filtered Then Zn(OAc)22H2O (283 mg 129 mmol) in CH3OH (10 mL) was added the

mixture was stirred at room temperature for 05 h Then the solvent was removed under reduced

pressure After addition of water and dichloromethane the organic phase was separated the

aqueous layer was extracted three times with CH2Cl2 the combined organic layer was dried over

MgSO4 and filtered The product was isolated by column chromatography (silica gel) using

CH2Cl2 as eluent Recrystallization from CH2Cl2CH3OH gave a red solid Yield 115 mg (76) 1H NMR (400 MHz CDCl3) δ 912 (d J = 46 Hz 2H) 896 (t 4H) 887 (d J = 47 Hz 2H)

842 (d J = 82 Hz 2H) 830 (d J = 80 Hz 2H) 822 (d J = 64 Hz 4H) 799 (d J = 84 Hz

2H) 784ndash767 (m 6H) 735 (d J = 88 Hz 4H) 729 (d J = 84 Hz 2H) 695 (d J = 89 Hz

4H) 410 (s 3H) 398 (t J = 65 Hz 4H) 187ndash171 (m 4H) 152ndash142 (m 4H) 141ndash116 (m

16H) 089 (t J = 66 Hz 6H) 13C NMR (101 MHz CDCl3) δ 16764 15595 15094 15054

15030 14982 14858 14805 14299 14101 13546 13466 13435 13262 13249 13214

13161 12952 12799 12776 12733 12679 12237 12147 11948 11807 11569 6855

5259 3205 2962 2948 2634 2289 1433 HRMS (MALDI-TOF) mz [M]+ calcd for

C74H71N5O4Zn 11574792 found 11574798 FT-IR (KBr) νmax 3042 2926 2855 1725 1603

1502 1278 1237 1001 cm-1

Synthesis of compound JY06 A mixture of porphyrin 6 (127 mg 011 mmol) and KOH

(056 g 10 mmol) in THFEtOHH2O (1101 50 ml) was refluxed for 12 h The mixture was

S7

then cooled to room temperature acidified with 01 M HCl to PH = 5 50 mL CH2Cl2 was added

The solution was washed three times with water and the combined organic layer was dried with

MgSO4 and removed by vacuo The residue was purified by flash column chromatography (silica

gel CH2Cl2CH3OH=101) to give JY06 as a red solid Yield 110 mg (87) 1H NMR (400 MHz

THF) δ 1164 (s 1H) 901 (d J = 46 Hz 2H) 891ndash873 (m 6H) 842 (d J = 81 Hz 2H) 829

(d J = 81 Hz 2H) 826ndash811 (m 4H) 798 (d J = 85 Hz 2H) 786ndash764 (m 6H) 742ndash718 (m

6H) 696 (d J = 90 Hz 4H) 399 (t J = 64 Hz 4H) 188ndash174 (m 4H) 160ndash145 (m 4H)

144ndash121 (m 16H) 102ndash076 (m 6H) 13C NMR (101 MHz THF) δ 16807 15721 15164

15123 15104 15067 14949 14925 14473 14193 13633 13593 13555 13547 13274

13261 13222 13191 13104 12871 12827 12815 12734 12256 12171 12008 11851

11635 6898 3300 3056 3054 3044 2728 2373 1460 HRMS (MALDI-TOF) mz [M]+

calcd for C73H69N5O4Zn 11434636 found 11434638 FT-IR (KBr) νmax 3041 2925 2854 1734

1693 1604 1502 1237 1001 cm-1 Anal Calcd For C73H69N5O4Zn C 7653 H 607 N 611

Found C 7639 H 602 N 609

S8

Fig S1 Fluorescence spectra of JY06 and JY07 in THF

Fig S2 Frontier orbitals of JY06 and JY07 (HOMO and LUMO)

Fig S3 FTIR spectra of (a) JY06 and (b) JY07 powders and stained TiO2 films

Fig S4 The photocurrent density-voltage (J-V) curves based on JY07 with and without CDCA

S9

Table S1 Photovoltaic performance for DSSCs based on JY07

dye CDCA (mM) Voc (V) Jsc (mAcm2) FF η () Γ (nmol cm-2)

JY07 0 065 1320 062 533 62

JY07 10 065 1220 061 485 45 aActive area 016 cm2 Electrolyte is composed of 03 M 12-dimethyl-3-propylimidazolium iodide (DMPII) 01

M LiI 005 M I2 and 05 M 4-tert -butyl pyridine in acetonitrile

Photostability study The long-term stability of DSSCs is a critical requirement for their photovoltaic application We

have used a straightforward method reported in literature to examine the stability of studied dyes5 For the stability study TiO2 thin films with areas of 1times1 cm2 and thicknesses of 3-4 μm were used

The films were immersed in a 03 mM solution of the porphyrin in THF for 05 h dried and the

absorbance was measured Then the same films were irradiated under standard one-sun

illumination for 5 min and 30 min and the absorbance was measured again

Fig S5 Absorption spectra of (a) JY06 and (b) JY07 that were adsorbed onto TiO2 films after

irradiation for 0 5 and 30 min

Fig S6 EIS spectra of DSSCs tested at -06 V forward bias in the dark (a) Nyquist and (b) Bode

phase plots

S10

References (1) J-W Ka and C-H Lee Tetrahedron Lett 2000 41 4609

(2) M Yoshida T Doi S Kang J Watanabe and T Takahashi Chem Commun 2009 2756

(3) J Mao N He Z Ning Q Zhang F Guo L Chen W Wu J Hua and H Tian Angew Chem

Int Ed 2012 51 9873

(4) Y Y Dou G R Li J Song and X P Gao Phys Chem Chem Phys 2012 14 1339

(5) (a) R B Ambre G-F Chang and C-H Hung Chem Commun 2014 50 725 (b) Y Wu M

Marszalek S M Zakeeruddin Q Zhang H Tian M Graumltzel and W Zhu Energy Environ

Sci 2012 5 8261 (c) R Katoh A Furube S Mori M Miyashita K Sunahara N Koumura

and K Hara Energy Environ Sci 2009 2 542

S11

1H NMR and 13C NMR spectra

Fig S7 1H NMR spectrum of compound 1 in CDCl3

Fig S8 13C NMR spectrum of compound 1 in CDCl3

S12

Fig S9 1H NMR spectrum of compound 2 in CDCl3

Fig S10 13C NMR spectrum of compound 2 in CDCl3

S13

Fig S11 1H NMR spectrum of compound 3 in CDCl3

Fig S12 13C NMR spectrum of compound 3 in CDCl3

S14

Fig S13 1H NMR spectrum of compound 4 in CDCl3

Fig S14 13C NMR spectrum of compound 4 in CDCl3

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 7: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S7

then cooled to room temperature acidified with 01 M HCl to PH = 5 50 mL CH2Cl2 was added

The solution was washed three times with water and the combined organic layer was dried with

MgSO4 and removed by vacuo The residue was purified by flash column chromatography (silica

gel CH2Cl2CH3OH=101) to give JY06 as a red solid Yield 110 mg (87) 1H NMR (400 MHz

THF) δ 1164 (s 1H) 901 (d J = 46 Hz 2H) 891ndash873 (m 6H) 842 (d J = 81 Hz 2H) 829

(d J = 81 Hz 2H) 826ndash811 (m 4H) 798 (d J = 85 Hz 2H) 786ndash764 (m 6H) 742ndash718 (m

6H) 696 (d J = 90 Hz 4H) 399 (t J = 64 Hz 4H) 188ndash174 (m 4H) 160ndash145 (m 4H)

144ndash121 (m 16H) 102ndash076 (m 6H) 13C NMR (101 MHz THF) δ 16807 15721 15164

15123 15104 15067 14949 14925 14473 14193 13633 13593 13555 13547 13274

13261 13222 13191 13104 12871 12827 12815 12734 12256 12171 12008 11851

11635 6898 3300 3056 3054 3044 2728 2373 1460 HRMS (MALDI-TOF) mz [M]+

calcd for C73H69N5O4Zn 11434636 found 11434638 FT-IR (KBr) νmax 3041 2925 2854 1734

1693 1604 1502 1237 1001 cm-1 Anal Calcd For C73H69N5O4Zn C 7653 H 607 N 611

Found C 7639 H 602 N 609

S8

Fig S1 Fluorescence spectra of JY06 and JY07 in THF

Fig S2 Frontier orbitals of JY06 and JY07 (HOMO and LUMO)

Fig S3 FTIR spectra of (a) JY06 and (b) JY07 powders and stained TiO2 films

Fig S4 The photocurrent density-voltage (J-V) curves based on JY07 with and without CDCA

S9

Table S1 Photovoltaic performance for DSSCs based on JY07

dye CDCA (mM) Voc (V) Jsc (mAcm2) FF η () Γ (nmol cm-2)

JY07 0 065 1320 062 533 62

JY07 10 065 1220 061 485 45 aActive area 016 cm2 Electrolyte is composed of 03 M 12-dimethyl-3-propylimidazolium iodide (DMPII) 01

M LiI 005 M I2 and 05 M 4-tert -butyl pyridine in acetonitrile

Photostability study The long-term stability of DSSCs is a critical requirement for their photovoltaic application We

have used a straightforward method reported in literature to examine the stability of studied dyes5 For the stability study TiO2 thin films with areas of 1times1 cm2 and thicknesses of 3-4 μm were used

The films were immersed in a 03 mM solution of the porphyrin in THF for 05 h dried and the

absorbance was measured Then the same films were irradiated under standard one-sun

illumination for 5 min and 30 min and the absorbance was measured again

Fig S5 Absorption spectra of (a) JY06 and (b) JY07 that were adsorbed onto TiO2 films after

irradiation for 0 5 and 30 min

Fig S6 EIS spectra of DSSCs tested at -06 V forward bias in the dark (a) Nyquist and (b) Bode

phase plots

S10

References (1) J-W Ka and C-H Lee Tetrahedron Lett 2000 41 4609

(2) M Yoshida T Doi S Kang J Watanabe and T Takahashi Chem Commun 2009 2756

(3) J Mao N He Z Ning Q Zhang F Guo L Chen W Wu J Hua and H Tian Angew Chem

Int Ed 2012 51 9873

(4) Y Y Dou G R Li J Song and X P Gao Phys Chem Chem Phys 2012 14 1339

(5) (a) R B Ambre G-F Chang and C-H Hung Chem Commun 2014 50 725 (b) Y Wu M

Marszalek S M Zakeeruddin Q Zhang H Tian M Graumltzel and W Zhu Energy Environ

Sci 2012 5 8261 (c) R Katoh A Furube S Mori M Miyashita K Sunahara N Koumura

and K Hara Energy Environ Sci 2009 2 542

S11

1H NMR and 13C NMR spectra

Fig S7 1H NMR spectrum of compound 1 in CDCl3

Fig S8 13C NMR spectrum of compound 1 in CDCl3

S12

Fig S9 1H NMR spectrum of compound 2 in CDCl3

Fig S10 13C NMR spectrum of compound 2 in CDCl3

S13

Fig S11 1H NMR spectrum of compound 3 in CDCl3

Fig S12 13C NMR spectrum of compound 3 in CDCl3

S14

Fig S13 1H NMR spectrum of compound 4 in CDCl3

Fig S14 13C NMR spectrum of compound 4 in CDCl3

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 8: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S8

Fig S1 Fluorescence spectra of JY06 and JY07 in THF

Fig S2 Frontier orbitals of JY06 and JY07 (HOMO and LUMO)

Fig S3 FTIR spectra of (a) JY06 and (b) JY07 powders and stained TiO2 films

Fig S4 The photocurrent density-voltage (J-V) curves based on JY07 with and without CDCA

S9

Table S1 Photovoltaic performance for DSSCs based on JY07

dye CDCA (mM) Voc (V) Jsc (mAcm2) FF η () Γ (nmol cm-2)

JY07 0 065 1320 062 533 62

JY07 10 065 1220 061 485 45 aActive area 016 cm2 Electrolyte is composed of 03 M 12-dimethyl-3-propylimidazolium iodide (DMPII) 01

M LiI 005 M I2 and 05 M 4-tert -butyl pyridine in acetonitrile

Photostability study The long-term stability of DSSCs is a critical requirement for their photovoltaic application We

have used a straightforward method reported in literature to examine the stability of studied dyes5 For the stability study TiO2 thin films with areas of 1times1 cm2 and thicknesses of 3-4 μm were used

The films were immersed in a 03 mM solution of the porphyrin in THF for 05 h dried and the

absorbance was measured Then the same films were irradiated under standard one-sun

illumination for 5 min and 30 min and the absorbance was measured again

Fig S5 Absorption spectra of (a) JY06 and (b) JY07 that were adsorbed onto TiO2 films after

irradiation for 0 5 and 30 min

Fig S6 EIS spectra of DSSCs tested at -06 V forward bias in the dark (a) Nyquist and (b) Bode

phase plots

S10

References (1) J-W Ka and C-H Lee Tetrahedron Lett 2000 41 4609

(2) M Yoshida T Doi S Kang J Watanabe and T Takahashi Chem Commun 2009 2756

(3) J Mao N He Z Ning Q Zhang F Guo L Chen W Wu J Hua and H Tian Angew Chem

Int Ed 2012 51 9873

(4) Y Y Dou G R Li J Song and X P Gao Phys Chem Chem Phys 2012 14 1339

(5) (a) R B Ambre G-F Chang and C-H Hung Chem Commun 2014 50 725 (b) Y Wu M

Marszalek S M Zakeeruddin Q Zhang H Tian M Graumltzel and W Zhu Energy Environ

Sci 2012 5 8261 (c) R Katoh A Furube S Mori M Miyashita K Sunahara N Koumura

and K Hara Energy Environ Sci 2009 2 542

S11

1H NMR and 13C NMR spectra

Fig S7 1H NMR spectrum of compound 1 in CDCl3

Fig S8 13C NMR spectrum of compound 1 in CDCl3

S12

Fig S9 1H NMR spectrum of compound 2 in CDCl3

Fig S10 13C NMR spectrum of compound 2 in CDCl3

S13

Fig S11 1H NMR spectrum of compound 3 in CDCl3

Fig S12 13C NMR spectrum of compound 3 in CDCl3

S14

Fig S13 1H NMR spectrum of compound 4 in CDCl3

Fig S14 13C NMR spectrum of compound 4 in CDCl3

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 9: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S9

Table S1 Photovoltaic performance for DSSCs based on JY07

dye CDCA (mM) Voc (V) Jsc (mAcm2) FF η () Γ (nmol cm-2)

JY07 0 065 1320 062 533 62

JY07 10 065 1220 061 485 45 aActive area 016 cm2 Electrolyte is composed of 03 M 12-dimethyl-3-propylimidazolium iodide (DMPII) 01

M LiI 005 M I2 and 05 M 4-tert -butyl pyridine in acetonitrile

Photostability study The long-term stability of DSSCs is a critical requirement for their photovoltaic application We

have used a straightforward method reported in literature to examine the stability of studied dyes5 For the stability study TiO2 thin films with areas of 1times1 cm2 and thicknesses of 3-4 μm were used

The films were immersed in a 03 mM solution of the porphyrin in THF for 05 h dried and the

absorbance was measured Then the same films were irradiated under standard one-sun

illumination for 5 min and 30 min and the absorbance was measured again

Fig S5 Absorption spectra of (a) JY06 and (b) JY07 that were adsorbed onto TiO2 films after

irradiation for 0 5 and 30 min

Fig S6 EIS spectra of DSSCs tested at -06 V forward bias in the dark (a) Nyquist and (b) Bode

phase plots

S10

References (1) J-W Ka and C-H Lee Tetrahedron Lett 2000 41 4609

(2) M Yoshida T Doi S Kang J Watanabe and T Takahashi Chem Commun 2009 2756

(3) J Mao N He Z Ning Q Zhang F Guo L Chen W Wu J Hua and H Tian Angew Chem

Int Ed 2012 51 9873

(4) Y Y Dou G R Li J Song and X P Gao Phys Chem Chem Phys 2012 14 1339

(5) (a) R B Ambre G-F Chang and C-H Hung Chem Commun 2014 50 725 (b) Y Wu M

Marszalek S M Zakeeruddin Q Zhang H Tian M Graumltzel and W Zhu Energy Environ

Sci 2012 5 8261 (c) R Katoh A Furube S Mori M Miyashita K Sunahara N Koumura

and K Hara Energy Environ Sci 2009 2 542

S11

1H NMR and 13C NMR spectra

Fig S7 1H NMR spectrum of compound 1 in CDCl3

Fig S8 13C NMR spectrum of compound 1 in CDCl3

S12

Fig S9 1H NMR spectrum of compound 2 in CDCl3

Fig S10 13C NMR spectrum of compound 2 in CDCl3

S13

Fig S11 1H NMR spectrum of compound 3 in CDCl3

Fig S12 13C NMR spectrum of compound 3 in CDCl3

S14

Fig S13 1H NMR spectrum of compound 4 in CDCl3

Fig S14 13C NMR spectrum of compound 4 in CDCl3

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

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S10

References (1) J-W Ka and C-H Lee Tetrahedron Lett 2000 41 4609

(2) M Yoshida T Doi S Kang J Watanabe and T Takahashi Chem Commun 2009 2756

(3) J Mao N He Z Ning Q Zhang F Guo L Chen W Wu J Hua and H Tian Angew Chem

Int Ed 2012 51 9873

(4) Y Y Dou G R Li J Song and X P Gao Phys Chem Chem Phys 2012 14 1339

(5) (a) R B Ambre G-F Chang and C-H Hung Chem Commun 2014 50 725 (b) Y Wu M

Marszalek S M Zakeeruddin Q Zhang H Tian M Graumltzel and W Zhu Energy Environ

Sci 2012 5 8261 (c) R Katoh A Furube S Mori M Miyashita K Sunahara N Koumura

and K Hara Energy Environ Sci 2009 2 542

S11

1H NMR and 13C NMR spectra

Fig S7 1H NMR spectrum of compound 1 in CDCl3

Fig S8 13C NMR spectrum of compound 1 in CDCl3

S12

Fig S9 1H NMR spectrum of compound 2 in CDCl3

Fig S10 13C NMR spectrum of compound 2 in CDCl3

S13

Fig S11 1H NMR spectrum of compound 3 in CDCl3

Fig S12 13C NMR spectrum of compound 3 in CDCl3

S14

Fig S13 1H NMR spectrum of compound 4 in CDCl3

Fig S14 13C NMR spectrum of compound 4 in CDCl3

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 11: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S11

1H NMR and 13C NMR spectra

Fig S7 1H NMR spectrum of compound 1 in CDCl3

Fig S8 13C NMR spectrum of compound 1 in CDCl3

S12

Fig S9 1H NMR spectrum of compound 2 in CDCl3

Fig S10 13C NMR spectrum of compound 2 in CDCl3

S13

Fig S11 1H NMR spectrum of compound 3 in CDCl3

Fig S12 13C NMR spectrum of compound 3 in CDCl3

S14

Fig S13 1H NMR spectrum of compound 4 in CDCl3

Fig S14 13C NMR spectrum of compound 4 in CDCl3

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 12: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S12

Fig S9 1H NMR spectrum of compound 2 in CDCl3

Fig S10 13C NMR spectrum of compound 2 in CDCl3

S13

Fig S11 1H NMR spectrum of compound 3 in CDCl3

Fig S12 13C NMR spectrum of compound 3 in CDCl3

S14

Fig S13 1H NMR spectrum of compound 4 in CDCl3

Fig S14 13C NMR spectrum of compound 4 in CDCl3

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 13: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S13

Fig S11 1H NMR spectrum of compound 3 in CDCl3

Fig S12 13C NMR spectrum of compound 3 in CDCl3

S14

Fig S13 1H NMR spectrum of compound 4 in CDCl3

Fig S14 13C NMR spectrum of compound 4 in CDCl3

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 14: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S14

Fig S13 1H NMR spectrum of compound 4 in CDCl3

Fig S14 13C NMR spectrum of compound 4 in CDCl3

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 15: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S15

Fig S15 1H NMR spectrum of compound JY07 in THF-d8

Fig S16 13C NMR spectrum of compound JY07 in THF-d8

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 16: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S16

Fig S17 1H NMR spectrum of compound 5 in CDCl3

Fig S18 13C NMR spectrum of compound 5 in CDCl3

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 17: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S17

Fig S19 1H NMR spectrum of compound 6 in CDCl3

Fig S20 13C NMR spectrum of compound 6 in CDCl3

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 18: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S18

Fig S21 1H NMR spectrum of compound JY06 in THF-d8

Fig S22 13C NMR spectrum of compound JY06 in THF-d8

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 19: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S19

HR-MS spectra

Fig S23 HR-MS spectrum of compound 1

Fig S24 HR-MS spectrum of compound 2

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 20: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S20

Fig S25 HR-MS spectrum of compound 3

Fig S26 HR-MS spectrum of compound 4

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 21: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S21

Fig S27 HR-MS spectrum of compound JY07

Fig S28 HR-MS spectrum of compound 5

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06

Page 22: Electronics Supplementary Information · commercial 20 nm TiO2 sol (China National Academy of Nanotechnology & Engineering) onto the treated FTO conductive glass (Nippon Sheet Glass,

S22

Fig S29 HR-MS spectrum of compound 6

Fig S30 HR-MS spectrum of compound JY06