Porphyrin sensitizers with modified indoline donors for dye-sensitized solar cells

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PAPER

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Nguyên T. K. Thanh, Xiaodi Su et al.

Fine-tuning of gold nanorod dimensions and plasmonic properties using

the Hofmeister eﬀects

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DOI: 10.1039/C8TC00610E

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Porphyrin Sensitizers with Modified Indoline Donors for Dye-

Sensitized Solar Cells

Heli Song,^aJing Zhang,^bJiamin Jin,^aHaifeng Wang^aand Yongshu Xie^*,a

Received 00th January 20xx,

Accepted 00th January 20xx

As a strong electron donor, indoline has been used in developing organic sensitizers for fabricating efficient dye-sensitized

solar cells. Herein we report porphyrin dyes based on modified indoline donors. Firstly, XW29 and XW31 featured with a

methylphenyl-substituted indoline and a bulkier dialkylfluorene-substituted indoline, respectively, are synthesized. XW31

exhibits a J_scof 22.06 mA·cm^-2as compared with that of 21.26 mA·cm^-2for XW29. Consequently, XW31 achieves a higher

power conversion efficiency of 10.46% than that of 10.14% for XW29. On this basis, to further broaden the spectral

response, a benzothiadiazole (BTD) unit is incorporated as the auxiliary electron acceptor to obtain XW30 and XW32,

respectively. The IPCE spectra are thus successfully extended to 850 nm. However, due to possibly aggravated dye

aggregation, charge recombination and less effective dye regeneration induced by the BTD unit, moderate efficiencies of

ca. 8.6% are obtained. Through coadsorption, elevated efficiencies of ~9.9% are achieved for XW30 and XW32. These

results provide further insights into developing efficient porphyrin dyes by combining the dialkylfluorene moiety with the

indoline donor.

DOI: 10.1039/x0xx00000x

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group has designed and synthesized a series of efficient

porphyrin dyes based on carbazole,^{20, 21}triphenylamine²²and

phenothiazine^23-25donors, respectively. In comparison to these

Introduction

As a type of photovoltaic device, dye-sensitized solar cells

(DSSCs) have created booming research interest over the past

two decades.¹Particularly, the quest for highly efficient

sensitizing dyes has never stopped. Compared with ruthenium

dyes and organic dyes,^2-5porphyrin dyes have the advantage

of relatively strong and broad absorption.⁶In fact, impressive

efficiencies have been achieved by porphyrin dyes such as

donors, indoline is another effective donor with strong

electron-donating ability, and it has been widely used in

organic sensitizers.^26-29However, its application in developing

porphyrin dyes is rather limited.^{30, 31}Herein, we report the

design and synthesis of four new porphyrin sensitizers XW29-

XW32 based on indoline donors (Fig. 1). With the purpose to

suppress dye aggregation and charge recombination, a bulky

dialkylfluorene moiety is attached to the N-atom of the

indoline unit. Meanwhile, the universal ethynyl benzoic acid

acceptor and the auxiliary benzothiadiazole (BTD) acceptor are

used to further investigate the effect of the acceptor on the

photovoltaic performance. By this porphyrin dye design

strategy and the application of chenodeoxycholic acid (CDCA)

as the coadsorbent, efficiencies over 10% are successfully

achieved. These results indicate that the introduction of a

dialkylfluorene substituent into the indoline donor is effective

for developing efficient porphyrin dyes.

YD2-o-C8 ⁷GY50⁸and the landmark molecule SM315 ⁹

, .

For designing efficient porphyrin sensitizers, it is essential to

broaden the absorption spectra for enhancing J_scand suppress

the unfavorable charge recombination for improving V_oc.^{10, 11}

The absorption band can be broadened by extending the π-

conjugation

framework

and/or

strengthening

the

intramolecular charge transfer (ICT) effect with suitable

electron donors, acceptors, and auxiliary acceptors.^12-16

However, a large conjugation framework is susceptible to dye-

aggregation and charge recombination, which are unfavorable

for the photovoltaic performance. To overcome this problem,

bulky alkyl chains can be introduced to suppress dye

aggregation and charge recombination.^17-19

With all the aforementioned considerations in mind, our

^aKey Laboratory for Advanced Materials and Institute of Fine Chemicals, Centre for

Computational Chemistry and Research Institute of Industrial Catalysis, School of

Chemistry and Molecular Engineering, East China University of Science and

Technology, Meilong 130, Shanghai 200237, China. *E-mail: yshxie@ecust.edu.cn

^bDepartment of Chemistry, Zhejiang University, Hangzhou 310028, P. R. China.

Electronic Supplementary Information (ESI) available: [details of any

supplementary information available should be included here]. See

DOI: 10.1039/x0xx00000x

Fig. 1 Molecular structures of XW29-XW32.

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DOI: 10.1039/C8TC00610E

t

Scheme 1. Synthetic routes for XW29-XW32. Reaction conditions: (i) 1-bromo-4-methylbenzene or 2-bromo-9,9-dibutyl-9H-fluorene, Pd(OAc)₂, P^tBu₃·HBF₄, BuONa, toluene; (ii)

NBS, acetone; (iii) trimethylsilylacetylene, Pd(PPh₃)₄, CuI, THF/Et₃N; (iv) KOH (1 M aq), THF/MeOH; (v) 4a or 4b, Pd₂(dba)₃, AsPh₃, THF/Et₃N; (vi) 4-ethynylbenzoic acid or 4-(7-

ethynylbenzo[c][1,2,5]thiadiazol-4-yl)benzoic acid, Pd(PPh₃)₄, CuI, THF, Et₃N or piperidine; (vii) LiOH·H₂O, THF/H₂O.

denoting a possibly aggravated H-type aggregation³²induced

by the benzothiadiazole unit. It is noteworthy that the

broadening character of the film absorption for all the four

Results and Discussion

Synthesis

dyes is favorable for improving the light-harvesting ability.

The synthetic routes for the dyes are illustrated in Scheme 1.

The details can be found in the experimental section. Firstly,

the

commercially

available

material

1,2,3,3a,4,8b-

hexahydrocyclopenta[b]indole successively underwent the

Buchwald-Hartwig reaction, bromination and the Sonogashira

reaction to obtain the ethynyl derivative of the indoline donor.

Then the zinc dibromoporphyrin was utilized as the platform

to attach the donor and acceptor to construct the D-π-A

framework. Finally the target products were obtained by

hydrolysis of the esters. All the dyes are air-stable and soluble

in common organic solvents such as CH₂Cl₂, CHCl₃, toluene and

THF.

Optical and Electrochemical Properties

Fig. 2 shows the UV-vis absorption spectra of the four dyes in

THF and on TiO₂films, and the corresponding data are

summarized in Table 1. The absorption maxima of XW29 are

located around 458 nm and 673 nm, which are red-shifted by

10 nm and 43 nm respectively compared to the reported

indoline-based porphyrin dye analogue CM-b³¹(448 nm and

630 nm) without the ethynylene group between the donor and

the porphyrin ring, showing the advantage of the ethynylene

linkage in light-harvesting. Compared to XW29, a tiny redshift

in the Q band can be observed for XW31, and the same trend

is observed for XW30 and XW32. These observations indicate

that the fluorene substituent on the N-atom of the indoline

donor may be slightly more electron-donating than the

methylphenyl unit. In contrast to XW29 and XW31, the BTD-

containing dyes XW30 and XW32 exhibit further red-shifted Q

Fig. 2. Absorption spectra of XW29-XW32 a) in THF solutions and b) on transparent TiO₂

films (~3 μm).

bands (Δλ

= ~20 nm), owing to the strong electron-

withdrawing effect of the BTD unit.

For all the four dyes, their absorption spectra on the TiO₂

films are slightly blue-shifted relative to those observed in THF

(Table 1) because of a combined effect of deprotonation and

aggregation. To make a clear comparison, the normalized

solution and film absorption spectra are shown in Fig. S2. As

compared with XW29 and XW31, more obvious blue shoulders

are observed for the films adsorbed with XW30 and XW32

,

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As shown in Fig. 4, the HOMOs of the four dyes are mainly

Table 1. Optical and Electrochemical Data for XW29-XW32.

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distributed on the indoline donor and^DOth^I:e¹⁰p^.1o⁰³r⁹p^/h^Cy⁸r^Ti^Cn⁰⁰c⁶o¹r⁰e^E,

while the LUMOs are delocalized through the porphyrin core

and the acceptor part. The appropriate charge separation and

overlapping characteristics may facilitate the electron transfer

from the donor to the acceptor and subsequent injection into

the TiO₂conduction band.

Absorption

λ_max/ nm (ε,

10³M^-1cm^-1)

458 (239.5),

673 (90.1)

467 (171.4),

693 (97.3)

455 (218.7),

674 (85.1)

468 (164.3),

695 (95.8)

E_ox^d/ V E_ox*^e/ V

b

c

λ_max

/

E_0-0

eV

/

a

(vs

nm

NHE)

0.83

NHE)

-1.00

XW29

XW30

XW31

XW32

457

1.83

1.75

1.82

1.75

463

451

462

0.84

0.85

0.86

-0.91

-0.97

-0.89

a

b

Absorption maxima in THF solutions (3 × 10^-6M). Absorption maxima on

transparent TiO₂films. ^cEstimated from the intersection wavelength (λ_inter) of the

normalized Q-band absorption and fluorescence emission spectra using the

equation E_0-0= 1240/λ_inter.

^dE_oxwas measured in acetonitrile using 0.1 M tetra-n-

butylammonium hexaﬂuorophosphate (TBAPF₆) as the electrolyte (working

electrode: FTO/TiO₂/dye; reference electrode: SCE; counter electrode: Pt) which

e

was calibrated with ferrocene/ferrocenium (Fc/Fc⁺) as an external reference.

Estimated from the equation E_ox* = E_ox- E_0-0

.

-

To confirm the compatibility of the dyes with TiO₂and the I₃

/I^-redox couple in terms of energy levels, cyclic voltammetry

curves were checked and the results are shown in Fig. S3, Fig.

3 and Table 1. Apparently, the experimentally determined

HOMO energy levels for the porphyrin dyes are located

between 0.83 V and 0.86 V (vs. NHE), which are more than 0.4

V more positive than the potential of I₃/I^-(~0.4 V vs. NHE).

-

Fig. 4 Frontier molecular orbital profiles and energy levels of XW29-XW32 calculated

by DFT.

Meanwhile, the LUMO levels range between -0.89 V and -1.00

V, which are more negative than the conduction band of TiO₂

(~-0.5 V vs. NHE), providing sufficient driving force for electron

injection. It should be noted that the HOMO levels of the four

dyes here are less positive than those of our previously

reported sensitizers based on phenothiazine donors (0.90

V~0.93 V),³³indicative of the stronger electron donating ability

of the indoline donor relative to phenothiazine.

Device Performance

DSSC devices were fabricated based on the porphyrin dyes.

Iodine-based electrolyte was used throughout the study. The

corresponding J-V curves are shown in Fig. 5 and the

photovoltaic parameters are summarized in Table 2.

Fig. 3 Schematic energy levels of XW29-XW32.

Theoretical Analysis

Density functional theory (DFT) calculations were performed

to gain insight into the molecular energy levels and frontier

molecular orbital distributions of the porphyrin dyes, using the

Gaussian 09 program package³⁴at the B3LYP/6-31G* level.^35-37

Fig. 5 a), b) J-V curves and c), d) IPCE action spectra of devices based on individual dyes

of XW29-XW32 in the absence/presence of 1 mM CDCA.

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Table 2 Photovoltaic parameters of the devices based on porphyrin dyes XW29-XW32 under simulated AM 1.5G full irradiation (100 mW·cm^-2). The active area is 0.12 cm². The

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DOI: 10.1039/C8TC00610E

data are the average values of four parallel devices. The last column shows the dye loading amount.

IPCE

SC

a

Dyes

XW29

XW30

XW31

XW32

CDCA

[mM]

V_oc

[mV]

J_sc

J

J_sc

FF

[%]

PCE^c

[%]

Dye loading

[mA·cm^-2]

[mAcm^-2]

18.97

18.38

16.59

17.92

19.99

18.44

17.26

18.38

error ^b

12%

20%

19%

20%

10%

19%

17%

19%

[nmol·cm^-2]

97

0

1

0

1

0

1

0

1

716 ± 4

701 ± 1

678 ± 1

688 ± 1

720 ± 4

696 ± 1

677 ± 2

688 ± 1

21.26 ± 0.41

22.00 ± 0.10

19.67 ± 0.29

21.48 ± 0.16

22.06 ± 0.30

21.98 ± 0.31

20.13 ± 0.20

21.89 ± 0.16

66.6 ± 0.3

65.0 ± 0.6

65.1 ± 1.0

66.8 ± 0.4

65.8 ± 1.0

65.0 ± 0.3

64.7 ± 0.4

65.9 ± 0.5

10.14 ± 0.13

10.04 ± 0.14

8.68 ± 0.09

9.87 ± 0.13

10.46 ± 0.19

9.94 ± 0.17

8.82 ± 0.14

9.94 ± 0.03

86

149

127

114

59

167

125

^aThe calculated J_scvalues by wavelength integration of the standard AM1.5G irradiation and the measured IPCE data. ^bThe relative deviation between the measured J_sc

and the calculated J_scvalues. ^cThe original data can be found in Table S1 and Table S2.

It is obvious that XW29 and XW31 featuring the devices, it is anticipated that XW30 and XW32 with broader

ethynylbenzoic acid acceptor afforded high efficiencies absorption would have slightly higher LHE values in

exceeding 10%, with V_ocvalues of 716 mV and 720 mV, and J_sccomparison to XW29 and XW31.^{9, 42}We then estimated the

values of 21.26 mA·cm^-2and 22.06 mA·cm^-2, respectively. electron injection efficiencies by means of the

These values are comparable to those for the porphyrin dyes photoluminescence (PL) decay measurements using the time-

with indoline donors reported by You and coworkers.³¹In correlated single-photon counting (TCSPC) technique.⁴⁵The

contrast, benzothiadiazole-containing dyes XW30 and XW32 values were estimated to be 85%, 92%, 81% and 94%,

afforded lower V_ocvalues of 678 mV and 677 mV as well as respectively (Fig. S4). We also estimated the charge collection

lower J_scvalues of 19.67 mA·cm^-2and 20.13 mA·cm^-2, efficiencies from the electrochemical impedance spectroscopy

respectively, resulting in lower PCEs of 8.68% and 8.82%, (EIS) analysis by using the equation η_coll= (1 + R_tr/R_rec)^-1.^46-48

respectively. The lower V_ocvalues observed for XW30 and The corresponding values at a bias potential of -0.70 V were

XW32 relative to XW29 and XW31 may be ascribed to the estimated to be 99% for XW29 and XW31 and 97% for XW30

aggravated dye aggregation and charge recombination effects and XW32, respectively (Fig. S5 and Table S3). The lower

induced by the auxiliary BTD unit (vide infra). The difference in charge collection efficiencies for XW30 and XW32 may

J_sccan be reflected in their IPCE spectra (Fig. 5c). Devices based indicate more serious charge recombination which may be

on XW29 and XW31 exhibit high IPCE plateaus, while those derived from their longer molecular lengths and possibly more

based on XW30 and XW32 exhibit broad but lower IPCEs. Such tilted adsorption orientation on the TiO₂surface (vide infra). It

a trend has also been observed in our previous systems.³⁸It is obvious that the different effects of the above-mentioned

should be noted that the IPCE tails of XW30 and XW32 extend three factors on the IPCE of the dyes with or without BTD are

beyond 850 nm, possibly indicative of relatively serious dye- in trade-off relationships, and the lower charge collection

aggregation.³⁹

efficiencies of XW30 and XW32 might not fully rationalize the

As a special note, the J_scvalues obtained from the J-V curves relatively lower IPCE and J_scvalues obtained for these two dyes.

are deviated within 20% compared to the theoretical values Hence, consistent with the lower J_scvalues for XW30 and

calculated from integrating the IPCE curves (Table 2), which is XW32, relatively lower dye regeneration efficiencies are

rather large, but still within a reasonably acceptable range.⁴⁰assumed for these two BTD-containing dyes, which is in

Theoretically, the deviation can be mainly ascribed to the accordance with the reported results indicating that the longer

following three reasons: 1) The reflection and absorption of molecular conjugation lengths of the dyes are correlated with

the FTO glass may account for ca. 10%~15% loss in the IPCE;^41,inferior dye regeneration efficiencies for the porphyrin-based

⁴²2) The full irradiation applied in the J-V test generates more DSSCs.⁴⁹

electrons and enables more efficient charge transport/

Based on the preceding results, we then used CDCA as the

collection than the wavelength-dependent light in the IPCE coadsorbent to suppress the dye-aggregation and charge

measurement;⁴³3) The full irradiation includes near-infrared recombination. The porphyrin dyes responded differently to

light and thus generates heat and an increase in temperature CDCA (Table 2). XW30 and XW32 afforded improved PCEs of

would lead to an increase in J_sc,^{43, 44}while the wavelength- approximately 9.9%, as a result of ~10 mV of V_ocincrease and

dependent light in the IPCE measurement barely exerts such 1.7~1.8 mA·cm^-2of J_scincrease, which agrees well with the

an effect.

It is known that the IPCE is mainly governed by four factors: XW29 and XW31

light-harvesting efficiency (LHE), electron injection efficiency photovoltaic performance, especially in terms of V_oc.

(φ_inj), charge collection efficiency (η_coll) and dye regeneration To further understand the device performance, the dye

elevated IPCE plateaus (Fig. 5c and 5d). On the contrary, for

,

CDCA unfavorably deteriorated their

efficiency (η_reg).⁷According to the absorption spectra on loading amounts were estimated spectroscopically by

transparent TiO₂films (Fig. 2b) and by considering the thicker desorbing the dyes into 0.1 M solutions of NaOH in THF/H₂O,

films with additional scattering layers used in the DSSC and the results are shown in Table 2. Interestingly, the

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dialkylfluorene-substituted molecules showed slightly higher

loading amounts than their methylphenyl-substituted

analogues. This observation may be related to the fact that the

additional alkyl chains attached to the fluorene unit might

improve the dye solubility and thus facilitate the dye-uptake.³²

A higher loading amount is beneficial for light-harvesting and

can improve J_scif the aggregation is not obviously aggravated.

Thus, it may partly account for the higher J_scof XW31 with

respect to XW29 device. On the other hand, much higher dye-

loading amounts were observed for XW30 and XW32 relative

to XW29 and XW31. However, lower J_scvalues were observed

for XW30 and XW32, probably indicating over-loading of the

dyes. After coadsorption with CDCA, the loading amounts for

all the four porphyrin dyes decreased because of the

competing adsorption of CDCA. Apparently, XW31 and XW32

show more dramatic decrease of loading amounts as

compared to XW29 and XW30, which could be rationalized by

their bulkier structure.

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Charge Extraction and Transient Photovoltage Decay

Measurements

To further understand the V_ocvariations for the DSSCs based

on the four porphyrin dyes, charge extraction (CE) and

transient photovoltage decay (TPD) measurements were

carried out.

As shown in Fig. 6a, at a certain open-circuit photovoltage,

the amount of charge extracted from different devices are

almost the same, implying similar positions of TiO₂conduction

Fig. 6 a) Correlation between the charge stored in a dye-grafted titania ﬁlm (Q^CE) and

the open-circuit photovoltage (V_OC) measured with the charge extraction (CE) method

TPD

and b) Comparison of electron half-lifetimes (t ) measured with the small-pulse

1/2

transient photovoltage decay (TPD) against Q^CE

.

band edges for the devices. On the other hand, the electron

Conclusions

TPD

half-lifetimes (t ) are quite different (Fig. 6b). For the

1/2

With the purpose to develop efficient DSSCs, we have

developed a series of indoline-based porphyrin dyes by

simultaneously modifying the electron donor and acceptor.

Specifically, methylphenyl and dialkylfluorene moieties were

respectively introduced into the indoline donor. For the

acceptor, the versatile ethynylbenzoic acid unit was used in

the absence or presence of the auxiliary benzothiadiazole

(BTD) acceptor. For XW29 and XW31 without the additional

BTD acceptor, high efficiencies exceeding 10% were achieved.

Compared with XW29, the introduction of the dialkylfluorene

unit in XW31 is favorable for improving the dye solubility and

elevating both the photovoltage and the photocurrent. As a

result, a higher PCE of 10.46% was achieved for XW31 relative

individual dye sensitized devices, the electron half-lifetimes for

the devices of XW29 and XW31 are much longer than those of

XW30 and XW32, indicative of less charge recombination of

XW29 and XW31, which is consistent with the EIS results (Fig.

S5). These results indicate that XW30 and XW32 might suffer

from more serious charge recombination due to a possibly

more tilted adsorption geometry associated with their

extended conjugation lengths.⁵⁰After coadsorption with CDCA,

devices based on XW30 and XW32 exhibit slightly prolonged

electron half-lifetimes, while those based on XW29 and XW31

show decreased electron half-lifetimes, which are in

accordance with the trend of their V_ocvariations. It could be

deduced that CDCA helps relieve the more serious aggregation

and charge recombination problems in the devices of XW30

and XW32, while it causes over-competing adsorption in those

to 10.16% for XW29

.

By introducing the auxiliary

benzothiadiazole (BTD) acceptor, the absorption spectra of

XW30 and XW32 were successfully extended, showing striking

IPCE wavelengths beyond 850 nm. In spite of the favorable

absorption, XW30 and XW32 exhibit lower efficiencies of

8.68%, and 8.82%, respectively, probably due to more serious

aggregation and charge recombination problems and less

effective dye regeneration. Fortunately, upon coadsorption

with CDCA, the corresponding efficiencies were improved to

9.87% and 9.94%, respectively. In summary, these results

provide further insights into developing efficient porphyrin

dyes by combining the dialkylfluorene moiety with the indoline

donor.

of XW29 and XW31

.

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The

starting

material

1,2,3,3a,4,8b-

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Experimental

Materials and instrumentation

hexahydrocyclopenta[b]indole

was ^DOp^I:u¹⁰rc^.1h⁰a³s⁹e^/Cd^8TC00fr⁶o¹⁰m^E

commercial source and used as received. 2-bromo-9,9-dibutyl-

9H-fluorene was prepared from 2-bromo-9H-fluorene

according to a reported method.⁵³

Compound 1a. It was prepared according to a procedure

modified from the literature report.³¹

1,2,3,3a,4,8b-hexahydrocyclopenta[b]indole (5.0 g, 31 mmol),

4-bromotoluene (5.37 g, 31 mmol), Pd(OAc)₂(176 mg, 0.78

mmol), P^tBu₃·HBF₄(455 mg, 1.6 mmol) and BuONa (4.2 g, 44

All reagents and solvents were purchased from commercial

sources of analytical grade and used as received unless

otherwise noted. Fluorine-doped SnO₂conducting glass (FTO

glass, transparency >90% in the visible range, sheet resistance

15Ω/square) was purchased from the Geao Science and

Educational Co. Ltd of China. TiO₂paste (18NR-T and 18NR-AO)

was purchased from Dyesol Ltd.

A mixture of

t

¹H NMR and ¹³C NMR spectra were obtained using a Bruker

AM 400 spectrometer at 298 K with tetramethylsilane (TMS)

used as the internal standard. HRMS measurements were

performed using a Waters LCT Premier XE spectrometer.

Matrix-assisted laser desorption/ionization time-of-ﬂight mass

mmol) in toluene (40 mL) was heated at 95°C under N₂for 9 h.

After cooling to room temperature, water was added and the

mixture was extracted with CH₂Cl₂. The combined organic

layers were dried over anhydrous Na₂SO₄, filtered and

concentrated in vacuo. The residue was purified by column

chromatography on silica gel (petroleum ether / CH₂Cl₂= 10 :

spectrometry (MALDI-TOF-MS) was measured using

a

1

Shimadzu-Kratos model Axima CFR+ mass spectrometer using

dithranol as the matrix. UV-Vis absorption spectra were

recorded on a Varian Cary 100 spectrophotometer and

fluorescence spectra were recorded on a Varian Cray Eclipse

fluorescence spectrophotometer. The cyclic voltammograms

of the dyes were performed on a Versastat II electrochemical

workstation (Princeton Applied Research) using 0.1 M TBAPF₆

(Adamas) as the supporting electrolyte, the sensitizer attached

to a nanocrystalline TiO₂ﬁlm deposited on the conducting FTO

glass as the working electrode, a platinum wire as the counter

electrode, and a regular calomel electrode in saturated KCl

solution as the reference electrode. The scan rate was fixed at

100 mV s^-1.

Photovoltaic measurements were performed by employing

an AM 1.5 solar simulator equipped with a 300 W xenon lamp

(model no. 91160, Oriel). The power of the simulated light was

calibrated to 100 mW cm^-2using a Newport Oriel PV reference

cell system (model 91150 V). J–V curves were obtained by

applying an external bias to the cell and measuring the

generated photocurrent with a model 2400 source meter

(Keithley Instruments, Inc. USA). The voltage step and delay

time of the photocurrent were 10 mV and 40 ms, respectively.

Action spectra of the incident monochromatic photon-to-

electron conversion efficiency (IPCE) for the solar cells were

1) to afford 1a as a colourless oil (7.1 g, 91%). H NMR (400

MHz, CDCl₃) δ 7.23 – 7.17 (m, 2H), 7.17 – 7.08 (m, 3H), 7.06 –

6.98 (m, 1H), 6.92 (d, J = 7.6 Hz, 1H), 4.80 – 4.70 (m, 1H), 3.87 –

3.78 (m, 1H), 2.34 (s, 3H), 2.09 – 1.98 (m, 1H), 1.96 – 1.84 (m,

2H), 1.84 – 1.75 (m, 2H), 1.70 – 1.61 (m, 1H), 1.58 – 1.49 (m,

1H).

Compound 1b ⁵⁴

. It was prepared as a white solid in a similar

way with 1a using 1,2,3,3a,4,8b-hexahydrocyclopenta[b]indole

(5.0 g, 31 mmol) and 2-bromo-9,9-dibutyl-9H-fluorene (11.2 g,

1

31 mmol) as the reactants (12.1 g, 88%). H NMR (400 MHz,

CDCl₃) δ 7.69 – 7.57 (m, 2H), 7.35 – 7.27 (m, 2H), 7.26 – 7.19

(m, 3H), 7.14 (d, J = 7.2 Hz, 1H), 7.10 – 7.03 (m, 1H), 7.03 – 6.96

(m, 1H), 6.79 – 6.68 (m, 1H), 4.90 – 4.80 (m, 1H), 3.92 – 3.80

(m, 1H), 2.12 – 1.78 (m, 7H), 1.72 – 1.61 (m, 1H), 1.27 – 1.21

(m, 1H), 1.16 – 1.01 (m, 4H), 0.93 – 0.81 (m, 3H), 0.73 – 0.62

(m, 8H).

Compound 2a. It was prepared according to a procedure

modified from the literature method.⁵⁵To a solution of 1a

(6.67 g, 26.7 mmol) in acetone (130 mL) was added an acetone

solution (50 mL) of NBS (4.76 g, 26.7 mmol) dropwise at 0°C.

Then the mixture was stirred at room temperature for 3 h and

then poured into water and extracted with CH₂Cl₂. The

combined organic layers were dried over anhydrous Na₂SO₄,

filtered and concentrated in vacuo. The residue was purified by

column chromatography on silica gel (petroleum ether / CH₂Cl₂

obtained with

Instruments). The intensity of monochromatic light was

measured with Si detector (Newport-71640). The

a

Newport-74125 system (Newport

1

= 10 : 1) to afford 2a as a white powder (8.3 g, 94%). H NMR

a

(400 MHz, CDCl₃) δ 7.19 – 7.11 (m, 5H), 7.08 (dd, J = 8.4, 1.6

Hz, 1H), 6.72 (d, J = 8.4 Hz, 1H), 4.78 – 4.70 (m 1H), 3.82 – 3.74

(m, 1H), 2.32 (s, 3H), 2.07 – 1.96 (m, 1H), 1.93 – 1.71 (m, 3H),

1.69 – 1.60 (m, 1H), 1.56 – 1.44 (m, 1H).

electrochemical impedance spectroscopy (EIS) measurements

of all the DSSCs were performed using a Zahner IM6e

Impedance Analyzer (ZAHNER-Elektrik GmbH

& CoKG,

Compound 2b ⁵⁶

It was prepared as a white powder in a

.

Kronach, Germany), with the frequency range of 0.1 Hz–100

kHz and the alternative signal of 10 mV. The ZSimpWin

software was used to ﬁt the experimental EIS data. TCSPC

measurements were performed on a LifeSpec-II fluorescence

spectrometer employing an EPL-670 pulsed laser diode and a

MCP high speed photomultiplier detector. The details for CE

and TPD measurements have been described in previous

papers.^{51, 52}

similar way with 2a using 1b (5.0 g, 11 mmol) as the starting

1

material (5.7 g, 96%). H NMR (400 MHz, CDCl₃) δ 7.67 – 7.58

(m, 2H), 7.34 – 7.28 (m, 2H), 7.26 – 7.23 (m, 1H), 7.23 – 7.17

(m, 3H), 7.15 – 7.10 (m, 1H), 6.83 (d, J = 8.4 Hz, 1H), 4.90 – 4.81

(m, 1H), 3.87 – 3.78 (m, 1H), 2.11 – 1.78 (m, 8H), 1.73 – 1.64

(m, 1H), 1.60 – 1.46 (m, 1H), 1.18 – 1.00 (m, 4H), 0.78 – 0.56

(m, 10H).

Compound 3a. To a solution of 2a (2.0 g, 6.1 mmol) in THF /

Et₃N (12 mL/48 mL) were added Pd(PPh₃)₄(352 mg, 0.30

mmol) and CuI (57 mg, 0.30 mol) under N₂. The mixture was

Syntheses of the dyes

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ARTICLE

stirred at 50°C under N₂before trimethylsilylacetylene (3.4 mL, = 6.4 Hz, 8H, -OCH₂-), 2.37 (s, 3H, phenylene-CH₃), 2.20 – 2.10

View Article Online

DOI: 10.1039/C8TC00610E

24 mmol) was added via a syringe over 20 min. Then the (m, 1H, indoline-CH₂-), 2.08 – 1.97 (m, 2H, indoline-CH₂-), 1.90

mixture was heated at 70°C for 22 h. The solvents were – 1.82 (m, 1H, indoline-CH₂-), 1.77 – 1.70 (m, 1H, indoline-CH₂-

removed in vacuo and the residue was purified by flash ), 1.68 – 1.60 (m, 1H, indoline-CH₂-), 1.23 – 1.16 (m, 8H), 1.14 –

column chromatography on silica gel (petroleum ether / CH₂Cl₂1.02 (m, 16H), 0.98 – 0.90 (m, 16H), 0.87 – 0.79 (m, 20H), 0.72

= 20 : 1) to afford 3a as a yellow oil (1.17 g, 55%).δ 7.21 – 7.18 – 0.63 (m, 8H), 0.59 – 0.47 (m, 16H), 0.46 – 0.36 (m, 8H). ¹³C

(m, 1H), 7.17 – 7.11 (m, 5H), 6.73 (d, J = 8.4 Hz, 1H), 4.79 – 4.72 NMR (101 MHz, CDCl₃) δ 159.97, 152.10, 151.08, 150.34,

(m, 1H), 3.79 – 3.70 (m, 1H), 2.32 (s, 3H), 2.03 – 1.91 (m, 1H), 148.94, 148.16, 139.98, 135.18, 132.16, 131.94, 131.89,

1.90 – 1.80 (m, 2H), 1.78 – 1.68 (m, 1H), 1.66 – 1.58 (m, 1H), 131.83, 131.49, 130.69, 129.85, 129.66, 127.79, 121.13,

1.53 – 1.42 (m, 1H), 0.23 (s, 9H). ¹³C NMR (101 MHz, CDCl₃) δ 120.46, 114.51, 113.47, 107.39, 105.08, 104.09, 100.83, 97.05,

148.16, 139.59, 134.43, 131.76, 131.73, 129.56, 128.01, 91.15, 69.27, 68.57, 64.56, 45.35, 35.20, 33.74, 31.87, 29.49,

120.28, 111.41, 106.62, 106.57, 90.62, 68.90, 44.88, 34.77, 29.38, 29.27, 29.10, 28.76, 28.65, 25.25, 24.46, 23.10, 22.66,

33.39, 24.07, 20.57. HRMS (ESI, m/z): [M+H]⁺calcd for 20.84, 14.11. HRMS (FTICR-MS) (m/z): [M+H]⁺calcd. for

C₂₃H₂₈NSi, 346.1991; found, 346.1990.

C₁₀₀H₁₃₃BrN₅O₄Zn, 1610.88269; found 1610.88843.

Compound 3b. It was prepared as a light orange powder in a

Compound 5b. It was prepared as a dark green tar in a

similar way with 3a using 2b (2.0 g, 3.9 mmol) as the starting similar way with 5a using the zinc dibromoporphyrin (700 mg,

1

material (1.2 g, 57%). H NMR (400 MHz, CDCl₃) δ 7.67 – 7.60 0.493 mmol) and 4b (245 mg) as the starting materials (159

1

(m, 2H), 7.34 – 7.28 (m, 2H), 7.27 – 7.26 (m, 1H), 7.25 – 7.18 mg, 18%). H NMR (400 MHz, CDCl₃) δ 9.69 (d, J = 4.4 Hz, 2H,

(m, 4H), 6.85 (d, J = 8.0 Hz, 1H), 4.92 – 4.84 (m, 1H), 3.85 – 3.77 pyrrolic), 9.56 (d, J = 4.8 Hz, 2H, pyrrolic), 8.85 (d, J = 4.4 Hz,

(m, 1H), 2.08 – 2.00 (m, 1H), 1.98 – 1.85 (m, 6H), 1.85 –1.76 2H, pyrrolic), 8.82 (d, J = 4.4 Hz, 2H, pyrrolic), 7.77 – 7.64 (m,

(m, 1H), 1.70 – 1.63 (m, 1H), 1.55 – 1.45 (m, 1H), 1.15 – 1.03 6H, phenyl), 7.38 – 7.26 (m, 5H, phenyl), 7.12 (d, J = 8.0 Hz, 1H,

(m, 4H), 0.74 – 0.59 (m, 10H), 0.24 (s, 9H). ¹³C NMR (101 MHz, phenyl), 6.99 (d, J = 8.4 Hz, 4H, phenyl), 5.05 – 4.97 (m, 1H,

CDCl₃) δ 151.77, 150.13, 147.84, 141.30, 140.72, 135.42, indoline-CH), 4.04 – 3.97 (m, 1H, indoline-CH), 3.83 (t, J = 6.4

134.74, 131.79, 128.10, 126.53, 125.96, 122.50, 120.00, Hz, 8H, -OCH₂-), 2.25 –2.15 (m, 1H), 2.12 – 2.06 (m, 1H), 2.04 –

118.76, 118.67, 114.42, 111.75, 107.01, 106.46, 90.87, 69.05, 1.97 (m, 4H), 1.94 – 1.86 (m, 1H), 1.80 – 1.72 (m, 1H), 1.71 –

54.71, 44.95, 39.96, 39.93, 34.75, 33.34, 25.76, 25.74, 24.15, 1.61 (m, 1H), 1.21 – 1.03 (m, 30H), 0.99 – 0.90 (m, 16H), 0.87 –

22.81, 13.63, 13.61. HRMS (ESI, m/z): [M+H]⁺calcd for 0.81 (m, 17H), 0.78 – 0.62 (m, 18H), 0.59 – 0.47 (m, 18H), 0.45

C₃₇H₄₆NSi, 532.3400; found, 532.3398.

– 0.35 (m, 8H). ¹³C NMR (101 MHz, CDCl₃) δ 159.97, 152.12,

Compound 4a. To a solution of 3a (470 mg, 1.36 mmol) in 152.08, 151.11, 150.39, 150.36, 148.97, 147.82, 141.70,

THF / MeOH (30 mL / 30 mL) was added dropwise an aqueous 141.04, 135.61, 135.46, 132.21, 131.97, 131.88, 131.49,

KOH solution (1 M, 1.36 mL) . The reaction mixture was 130.70, 129.69, 127.87, 126.79, 126.18, 122.75, 121.11,

allowed to stir at room temperature for 4.5 h. Then water was 120.30, 119.00, 118.91, 114.58, 113.82, 107.79, 105.11,

added and the mixture was extracted with CH₂Cl₂, washed 104.16, 100.79, 96.98, 91.31, 69.43, 68.59, 64.63, 55.00, 45.41,

with brine, dried over Na₂SO₄and evaporated in vacuo to 40.27, 40.23, 35.17, 33.68, 31.86, 29.48, 29.37, 29.27, 29.09,

afford the crude product of 4a as a yellow oil (330 mg), which 28.75, 28.65, 26.06, 26.03, 25.25, 24.53, 23.15, 23.09, 22.67,

was extremely unstable on silica gel and was therefore directly 14.12, 13.90, 13.87. HRMS (FTICR-MS) (m/z): [M+H]⁺calcd. for

used for the next step without further purification.

C₁₁₄H₁₅₁BrN₅O₄Zn, 1797.0235; found 1797.0241.

Compound 4b. It was prepared in a similar way with 4a using

Compound 6a. To a mixture of 5a (80 mg, 0.050 mmol) and

3b (664 mg, 1.25 mmol) as the starting material and the crude methyl 4-ethynylbenzoate (24 mg, 0.15 mmol) in THF / Et₃N

product was obtained as a light orange powder (560 mg), (24 mL / 4 mL) were added Pd(PPh₃)₄(29 mg, 0.025 mmol) and

which was also unstable on silica gel and was thus directly CuI (5 mg, 0.025 mmol) under N₂. The mixture was stirred at

used for the next step without further purification.

60°C under N₂for 24 h. Then solvents were removed in vacuo

Compound 5a. To a mixture of the zinc dibromoporphyrin and the residue was purified by column chromatography on

(727 mg, 0.51 mmol) and the crude product of 4a (155 mg) in silica gel (petroleum ether / CH₂Cl₂= 1.2 : 1) and then on a

THF / Et₃N (200 mL / 50 mL) were added Pd₂(dba)₃(234 mg, preparative silica gel plate (petroleum ether / THF = 9 : 1) to

0.26 mmol) and AsPh₃(313 mg, 1.02 mmol) under N₂. The give the crude product, which was recrystallized from CH₂Cl₂/

1

mixture was allowed to stir at 50°C under N₂for 4.5 h. Then MeOH to give 6a as a dark green solid (40 mg, 48%). H NMR

solvents were removed in vacuo and the residue was purified (400 MHz, CDCl₃) δ 9.67 (d, J = 4.4 Hz, 2H, pyrrolic), 9.61 (d, J =

by column chromatography on silica gel (petroleum ether / 4.4 Hz, 2H, pyrrolic), 8.87 (d, J = 4.8 Hz, 2H, pyrrolic), 8.83 (d, J

CH₂Cl₂= 2 : 1) and then on a preparative silica gel plate = 4.4 Hz, 2H, pyrrolic), 8.13 (d, J = 8.0 Hz, 2H, phenyl), 7.97 (d, J

(petroleum ether / THF = 25 : 1) to afford 5a as a dark green = 8.0 Hz, 2H, phenyl), 7.76 – 7.63 (m, 5H, phenyl), 7.27 (d, J =

1

tar (173 mg, 21%). H NMR (400 MHz, CDCl₃) δ 9.67 (d, J = 4.4 8.0 Hz, 1H, phenyl), 7.21 (d, J = 8.3 Hz, 2H, phenyl), 7.04 – 6.96

Hz, 2H, pyrrolic), 9.55 (d, J = 4.8 Hz, 2H, pyrrolic), 8.83 (d, J = (m, 5H, phenyl), 4.94 – 4.87 (m, 1H, indoline-CH), 4.00 – 3.92

4.4 Hz, 2H, pyrrolic), 8.81 (d, J = 4.4 Hz, 2H, pyrrolic), 7.75 – (m, 4H, indoline-CH and -OCH₃), 3.85 (t, J = 6.4 Hz, 8H, -OCH₂-),

7.64 (m, 4H, phenyl), 7.27 (d, J = 8.4 Hz, 2H, phenyl), 7.21 (d, J 2.37 (s, 3H, phenylene-CH₃), 2.20 – 2.11 (m, 1H, indoline-CH₂-),

= 8.4 Hz, 2H, phenyl), 7.04 – 6.95 (m, 5H, phenyl), 4.94 – 4.86 2.08 – 1.96 (m, 2H, indoline-CH₂-), 1.89 – 1.80 (m, 1H, indoline-

(m, 1H, indoline-CH), 4.00 – 3.93 (m, 1H, indoline-CH), 3.83 (t, J CH₂-), 1.77 – 1.71 (m, 1H, indoline-CH₂-), 1.68 – 1.60 (m, 1H,

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indoline-CH₂-), 1.20 – 1.12 (m, 8H), 1.09 – 0.95 (m, 24H), 0.92 – 130.25, 129.80, 129.44, 129.04, 128.55, 12 7_V.8_iew5,_Arti1_cl2_e6_O._n7_lin9_e,

0.85 (m, 8H), 0.83 – 0.75 (m, 20H), 0.66 – 0.58 (m, 8H), 0.57 – 126.20, 122.75, 120.89, 120.30, 119^D.0^O1^I,^{: 10}1^.11⁰5³.⁹3^/9^C,^8TC1⁰1⁰4⁶.6¹⁰4^E,

0.36 (m, 24H). ¹³C NMR (101 MHz, CDCl₃) δ 166.48, 159.93, 113.44, 107.71, 105.18, 102.73, 98.55, 97.78, 96.70, 94.56,

151.85, 151.40, 150.52, 150.34, 148.29, 139.87, 135.16, 91.11, 69.41, 68.65, 55.00, 52.16, 45.33, 40.28, 40.23, 35.20,

135.10, 135.04, 132.06, 131.96, 131.61, 131.49, 131.27, 33.62, 31.83, 29.45, 29.34, 29.24, 29.23, 29.08, 28.71, 28.63,

130.85, 130.23, 129.84, 129.80, 129.45, 129.07, 128.57, 26.05, 26.02, 25.27, 24.50, 23.10, 22.64, 14.09, 13.92, 13.88.

128.28, 128.22, 128.16, 127.79, 120.92, 120.54, 115.39, HRMS (FTICR-MS) (m/z): [M]⁺calcd. for C₁₂₄H₁₅₇N₅O₆Zn,

113.10, 107.31, 105.21, 102.87, 98.51, 97.95, 96.70, 94.56, 1876.1420; found 1876.1401.

90.91, 69.26, 68.66, 52.15, 45.28, 35.23, 33.69, 31.84, 29.70,

Compound 6d. It was synthesized in the same procedure as

29.45, 29.34, 29.23, 29.08, 28.71, 28.63, 25.27, 24.44, 22.64, 6a except that 5b (120 mg, 0.067 mmol) and methyl 4-(7-

20.84, 14.08. HRMS (FTICR-MS) (m/z): [M]⁺calcd. for ethynylbenzo[c][1,2,5]thiadiazol-4-yl) benzoate (49 mg, 0.17

C₁₁₀H₁₃₉N₅O₆Zn, 1690.0011; found 1690.0016.

mmol) were used as the reactants and THF/piperidine (20 mL /

Compound 6c. It was synthesized in the same procedure as 1 mL) were used as the solvents. The product was obtained as

1

6a except that 5a (105 mg, 0.065 mmol) and methyl 4-(7- a brownish-green powder (37 mg, 27%). H NMR (400 MHz,

ethynylbenzo[c][1,2,5]thiadiazol-4-yl)benzoate (48 mg, 0.16 CDCl₃) δ 9.86 (d, J = 4.4 Hz, 2H, pyrrolic), 9.63 (d, J = 4.4 Hz, 2H,

mmol) were used as the reactants and THF/piperidine (20 mL / pyrrolic), 8.90 (d, J = 4.4 Hz, 2H, pyrrolic), 8.84 (d, J = 4.4 Hz,

1 mL) were used as the solvents. The product was obtained as 2H, pyrrolic), 7.99 (d, J = 7.2 Hz, 1H, phenyl), 7.80 (d, J = 8.0 Hz,

a brownish-green solid (35 mg, 29%). ¹H NMR (400 MHz, 2H, phenyl), 7.76 – 7.62 (m, 8H, phenyl), 7.43 (d, J = 7.2 Hz, 1H,

CDCl₃) δ 9.97 (d, J = 4.4 Hz, 2H, pyrrolic), 9.66 (d, J = 4.4 Hz, 2H, phenyl), 7.39 – 7.25 (m, 5H, phenyl), 7.10 (d, J = 8.0 Hz, 1H,

pyrrolic), 8.93 (d, J = 4.8 Hz, 2H, pyrrolic), 8.84 (d, J = 4.4 Hz, phenyl), 7.04 (d, J = 8.8 Hz, 4H, phenyl), 5.02 (t, J = 7.0 Hz, 1H,

2H, pyrrolic), 8.21 (d, J = 7.2 Hz, 1H, phenyl), 8.15 (d, J = 8.4 Hz, indoline-CH), 4.00 (t, J = 8.0 Hz, 1H, indoline-CH), 3.95 – 3.83

2H, phenyl), 8.05 (d, J = 8.0 Hz, 2H, phenyl), 7.82 (d, J = 7.2 Hz, (m, 11H, -OCH₂- and -OCH₃), 2.26 – 2.14 (m, 1H), 2.12 – 2.06

1H, phenyl), 7.76 – 7.64 (m, 4H, phenyl), 7.27 (d, J = 8.4 Hz, 2H, (m, 1H), 2.04 – 1.97 (m, 4H), 1.95 – 1.86 (m, 1H), 1.82 – 1.73

phenyl), 7.22 (d, J = 8.4 Hz, 2H, phenyl), 7.06 – 6.97 (m, 5H, (m, 1H), 1.72 – 1.62 (m, 1H), 1.32 – 1.27 (m, 2H), 1.20 – 1.08

phenyl), 4.95 – 4.87 (m, 1H, indoline-CH), 4.03 – 3.93 (m, 4H, (m, 12H), 1.08 – 0.93 (m, 24H), 0.92 – 0.83 (m, 10H), 0.82 –

indoline-CH and -OCH₃), 3.87 (t, J = 6.4 Hz, 8H, -OCH₂-), 2.38 (s, 0.71 (m, 27H), 0.69 – 0.63 (m, 8H), 0.62 – 0.45 (m, 24H). ¹³C

3H, phenylene-CH), 2.24 – 1.94 (m, 4H), 1.89 – 1.80 (m, 1H), NMR (101 MHz, CDCl₃) δ 166.56, 159.97, 155.66, 152.40,

1.77 – 1.71 (m, 1H), 1.68 – 1.60 (m, 1H), 1.18 – 0.92 (m, 32H), 152.12, 151.21, 150.47, 150.31, 148.22, 140.27, 139.87,

0.90 – 0.72 (m, 28H), 0.67 – 0.36 (m, 31H). ¹³C NMR (101 MHz, 135.15, 132.19, 131.89, 131.60, 131.33, 130.77, 130.68,

CDCl₃) δ 166.62, 159.97, 155.76, 152.55, 152.14, 152.08, 130.58, 130.53, 129.83, 129.76, 129.11, 128.79, 128.04,

151.22, 150.47, 150.39, 150.32, 147.87, 141.64, 141.04, 127.79, 127.73, 120.93, 120.45, 117.91, 115.49, 113.14,

140.50, 135.62, 135.45, 132.13, 131.58, 131.28, 130.71, 107.31, 105.15, 102.89, 101.64, 98.41, 97.86, 92.23, 90.98,

130.59, 129.73, 129.23, 128.94, 128.22, 127.88, 126.80, 69.23, 68.70, 52.13, 45.29, 35.23, 33.70, 31.80, 29.44, 29.35,

126.19, 122.76, 121.06, 120.31, 119.01, 118.95, 118.10, 29.25, 29.21, 29.12, 28.77, 28.68, 25.33, 24.45, 22.60, 20.85,

115.37, 114.61, 113.62, 107.74, 105.19, 102.70, 101.98, 98.33, 14.06. HRMS (FTICR-MS) (m/z): [M]⁺calcd. for

97.66, 92.22, 91.34, 69.42, 68.71, 55.01, 52.14, 48.79, 45.37, C₁₃₀H₁₅₉N₇O₆SZn, 2010.1359; found 2010.1331.

40.28, 35.20, 33.65, 31.81, 29.46, 29.37, 29.27, 29.22, 29.13,

XW29. To a solution of 6a (54 mg, 0.032 mmol) in THF (20

28.79, 28.69, 26.07, 26.04, 25.31, 24.53, 23.10, 22.61, 14.06, mL) was added a solution of LiOH·H₂O (54 mg, 1.3 mmol) in

13.92, 13.88. HRMS (FTICR-MS) (m/z): [M]⁺calcd. for H₂O (2 mL). The mixture was stirred at 55°C under N₂for 18 h.

C₁₁₆H₁₄₁N₇O₆SZn, 1823.9950; found 1823.9939.

After cooling to room temperature, water was added and the

Compound 6b. It was synthesized in the same procedure as mixture was extracted with CH₂Cl₂. The combined organic

6a using 5b (95 mg, 0.053 mmol) as the starting material and it layers were dried over Na₂SO₄and evaporated in vacuo. The

1

was obtained as a dark green powder (55 mg, 55%). H NMR residue was then purified on a preparative silica gel plate

(400 MHz, CDCl₃) δ 9.69 (d, J = 4.4 Hz, 2H, pyrrolic), 9.63 (d, J = (CH₂Cl₂/ MeOH = 15 : 1) to afford the crude product, which

4.4 Hz, 2H, pyrrolic), 8.87 (d, J = 4.8 Hz, 2H, pyrrolic), 8.84 (d, J was recrystallized from CH₂Cl₂/ MeOH to give XW29 as a dark

= 4.4 Hz, 2H, pyrrolic), 8.18 (d, J = 8.4 Hz, 2H, phenyl), 8.01 (d, J green powder (43 mg, 79%). ¹H NMR (400 MHz, CDCl₃: DMSO-

= 8.4 Hz, 2H, phenyl), 7.78 – 7.63 (m, 6H, phenyl), 7.38 – 7.27 d₆= 1:2, v/v) δ 12.94 (br, 1H, -COOH), 9.52 (d, J = 4.4 Hz, 4H,

(m, 5H, phenyl), 7.12 (d, J = 8.0 Hz, 1H, phenyl), 7.01 (d, J = 8.4 pyrrolic), 8.70 (d, J = 4.4 Hz, 2H, pyrrolic), 8.67 (d, J = 4.4 Hz,

Hz, 4H, phenyl), 5.05 – 4.98 (m, 1H, indoline-CH), 4.05 – 3.96 2H, pyrrolic), 8.18 – 8.13 (m, 2H, phenyl), 8.06 (d, J = 8.4 Hz,

(m, 4H, indoline-CH and –OCH₃), 3.85 (t, J = 6.4 Hz, 8H, -OCH₂-), 2H, phenyl), 7.76 – 7.61 (m, 4H, phenyl), 7.30 – 7.18 (m, 4H,

2.25 – 2.16 (m, 1H), 2.14 – 2.04 (m, 2H), 2.04 – 1.96 (m, 4H), phenyl), 7.06 (d, J = 8.4 Hz, 4H, phenyl), 6.98 (d, J = 8.4 Hz, 1H,

1.95 – 1.86 (m, 1H), 1.81 – 1.73 (m, 1H), 1.72 – 1.64 (m, 1H), phenyl), 5.01 – 4.93 (m, 1H, indoline -CH), 4.00 – 3.94 (m, 1H,

1.21 – 1.11 (m, 12H), 1.10 – 0.94 (m, 24H), 0.93 – 0.83 (m, indoline -CH), 3.87 (t, J = 6.4 Hz, 8H, -OCH₂-), 2.34 (s, 3H,

10H), 0.82 – 0.68 (m, 28H), 0.66 – 0.58 (m, 8H), 0.57 – 0.32 (m, phenylene-CH₃), 2.22 – 2.10 (m, 1H, indoline -CH₂-), 2.04 – 1.95

24H). ¹³C NMR (101 MHz, CDCl₃) δ 166.47, 159.92, 152.07, (m, 1H, indoline -CH₂-), 1.92 – 1.81 (m, 2H, indoline -CH₂-), 1.77

151.84, 151.39, 150.52, 150.39, 150.35, 147.92, 141.59, – 1.68 (m, 1H, indoline -CH₂-), 1.60 – 1.49 (m, 1H, indoline -

141.03, 135.65, 135.45, 132.05, 131.59, 131.50, 130.83, CH₂-), 1.21 – 1.12 (m, 8H), 1.11 – 1.01 (m, 16H), 1.01 – 0.87 (m,

J. Name., 2013, 00, 1-3 | 8

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24H), 0.85 – 0.73 (m, 20H), 0.66 – 0.50 (m, 16H), 0.45 – 0.31 for 20 minutes under ultrasonication befor_Ve_iewu_Ars_te_icl._{e O}T_nlh_ine_e

(m, 8H). HRMS (FTICR-MS) (m/z): [M]⁺calcd. for preparation of the TiO₂electrodes and f^Da^Obr^I:ic¹⁰a^.t¹i⁰o³n^9/o^Cf^8Tth^Ce⁰⁰c⁶e¹⁰ll^Es

C₁₀₉H₁₃₇N₅O₆Zn, 1675.9855; found 1675.9836.

were adapted from that reported by Grꢀtzel and co-workers.⁵⁷

XW30. It was synthesized in the same procedure as XW29 The photoanode was prepared by repetitive screen-printing.

using 6c (60 mg, 0.033 mmol) as the starting material, and it Afterwards, the TiO₂films were heated with a programmed

1

was obtained as a brownish-green powder (50 mg, 83%). H procedure at 275 °C for 5 min, 325 °C for 5 min, 375 °C for 5

NMR (400 MHz, CDCl₃: DMSO-d₆= 1 : 2) δ 12.93 (br, 1H, - min, 450 °C for 15 min, and 500 °C for 15 min. The resulting

COOH), 9.88 (d, J = 4.8 Hz, 2H, pyrrolic), 9.52 (d, J = 4.4 Hz, 2H, layers were post-treated with 40 mM TiCl₄solution at 70 °C for

pyrrolic), 8.77 (d, J = 4.4 Hz, 2H, pyrrolic), 8.68 (d, J = 4.4 Hz, 30 min and sintered once again at 450 °C for 30 min. Then they

2H, pyrrolic), 8.38 (d, J = 7.2 Hz, 1H, phenyl), 8.25 (d, J = 8.4 Hz, were immersed in a 0.1 mM solution of the dyes in a mixture

2H, phenyl), 8.17 (d, J = 7.2 Hz, 2H, phenyl), 8.13 (d, J = 7.2 Hz, of CHCl₃and ethanol (2:3, v/v) for 10 h at 25 °C for dye loading.

1H, phenyl), 7.76 – 7.68 (m, 3H, phenyl), 7.66 (d, J = 8.4 Hz, 1H, For coadsorption, chenodeoxycholic acid was added into the

phenyl), 7.27 (d, J = 8.4 Hz, 2H, phenyl), 7.22 (d, J = 8.4 Hz, 2H, dye solution as above mentioned. For the counter electrode,

phenyl), 7.07 (d, J = 8.4 Hz, 4H, phenyl), 6.98 (d, J = 8.4 Hz, 1H, H₂PtCl₆in 2-propanol solution was uniformly distributed on

phenyl), 5.01 – 4.94 (m, 1H, indoline-CH), 4.00 – 3.94 (m, 1H, FTO glass through spin coating, and the cathode was heated at

indoline-CH), 3.88 (t, J = 5.6 Hz, 8H, -OCH₂-), 2.35 (s, 3H, 400 °C for deposition of platinum. Eventually, the two

phenylene-CH₃), 2.22 – 2.12 (m, 1H, indoline-CH₂-), 2.02 – 1.96 electrodes were sealed with thermoplastic Surlyn, and an

(m, 1H, indoline-CH₂-), 1.92 – 1.82 (m, 2H, indoline-CH₂-), 1.77 electrolyte solution was injected through one hole in the

– 1.69 (m, 1H, indoline-CH₂-), 1.60 – 1.50 (m, 1H, indoline-CH₂- counter electrode to complete the sandwich-type solar cells.

), 1.15 – 1.07 (m, 8H), 1.04 – 0.85 (m, 40H), 0.81 – 0.70 (m, The electrolyte was composed of 0.1 M LiI, 0.05 M I₂, 1.0 M 1,

20H), 0.66 – 0.52 (m, 16H), 0.44 – 0.34 (m, 8H). HRMS (FTICR- 2-dimethyl-3-propyl-imidazolium iodide (DMPII) and 0.5 M 4-

MS) (m/z): [M]⁺calcd. for C₁₁₅H₁₃₉N₇O₆SZn, 1809.9794; found tert-butylpyridine (TBP) in acetonitrile.

1809.9759.

XW31. It was synthesized in the same procedure as XW29

Conflicts of interest

There are no conflicts to declare.

using 6b (64 mg, 0.034 mmol) as the starting material, and it

1

was obtained as a dark green powder (49 mg, 78%). H NMR

(400 MHz, CDCl₃: DMSO-d₆= 1 : 2, v / v) δ 13.02 (br, 1H, -

COOH), 9.57 – 9.49 (m, 4H, pyrrolic), 8.70 (d, J = 4.4 Hz, 2H,

pyrrolic), 8.67 (d, J = 4.0 Hz, 2H, pyrrolic), 8.17 (d, J = 8.0 Hz,

2H, phenyl), 8.05 (d, J = 8.0 Hz, 2H, phenyl), 7.82 – 7.66 (m, 6H,

phenyl), 7.42 – 7.24 (m, 5H, phenyl), 7.15 – 7.00 (m, 5H,

phenyl), 5.14 – 5.04 (m, 1H, indoline -CH), 4.04 – 3.97 (m, 1H,

indoline -CH), 3.93 – 3.78 (m, 8H, -OCH₂-), 2.24 – 2.16 (m, 1H),

2.08 – 1.97 (m, 5H), 1.96 – 1.88 (m, 2H), 1.79 – 1.72 (m, 1H),

1.61 – 1.54 (m, 1H), 1.18 – 0.92 (m, 52H), 0.82 – 0.53 (m, 46H),

0.43 – 0.30 (m, 8H). HRMS (FTICR-MS) (m/z): [M]⁺calcd. for

C₁₂₃H₁₅₅N₅O₆Zn, 1862.1263; found 1862.1248.

Acknowledgements

This work was ﬁnancially supported by NSFC (21472047,

21772041), the Program for Professor of Special Appointment

(Eastern Scholar, GZ2016006) at Shanghai Institutions of

Higher Learning, and the Fundamental Research Funds for the

Central Universities (WK1616004, 222201717003).

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View Article Online

DOI: 10.1039/C8TC00610E

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Page 12 of 12

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DOI: 10.1039/C8TC00610E

Graphical abstract

A high power conversion efficiency exceeding 10% was achieved for novel porphyrin

sensitizers with modified indoline donors.

Article Doi

Porphyrin sensitizers with modified indoline donors for dye-sensitized solar cells

DOI: 10.1039/c8tc00610e

Source and publish data:

Authors:

Article abstract of DOI:10.1039/c8tc00610e

Full text of DOI:10.1039/c8tc00610e

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