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Physical Chemistry Chemical Physics
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General synthesis of compound 4a-d: The solution of 167.6, 153.5, 152.3, 147.6, 141.4, 141.2, 140.0, 139.6, 135.9,
DOI: 10.1039/C9CP00091G
compound 3 (0.60 mmol) in acetone (30 mL) was added NBS 135.1, 131.3, 130.6, 130.3, 130.0, 129.6, 128.4, 126.8, 125.4,
(0.66 mmol) in 5 mL acetone. The mixture was stirred for 3 h at 123.8, 120.1, 107.4, 68.7, 45.0, 35.4, 33.6, 24.5, 22.3, 20.9, 15.8.
r.t., then the water was added and the reaction mixture was HRMS (TOF MS ES+): m/z calcd for C37H31N3O2S2 [M+H]+
extracted with ethyl acetate. The combined organic layer was 613.1858, found 613.1864.
dried over anhydrous Na2SO4, and evaporated under reduced
Characterization of CS-28: 1H NMR (500 MHz, d6-DMSO,
pressure. The crude product was dissolved in dry THF (20 mL) ppm): δ 13.12 (s, 1H), 8.12-8.21 (m, 6H), 8.01 (d, J = 9.0 Hz, 1H),
and the solution was cooled to -78 ºC, then n-BuLi (2M, 2mL) 7.20-7.27 (m, 5H), 7.15 (d, J = 10.0 Hz, 1H), 6.95 (d, J = 10.0 Hz,
was added. The triisopropyl borate (0.28 g,1.492mmol) was 1H), 4.91-4.95 (m, 1H), 3.87-3.91 (m, 1H), 2.78-2.91 (m, 1H),
slowly added after the mixture was stirred for 2 h. Then the 2.31 (s, 3H), 2.05-2.15 (m, 1H), 1.65-1.86 (m, 10H), 1.24-1.47 (m,
reaction mixture was warmed to r.t. and stirred for another 12 5H). 13C NMR (125 MHz, d6-DMSO, ppm): δ 167.6, 153.5, 153.5,
h. After the reaction was completed, water was added and the 152.3, 147.6, 147.6, 143.9, 141.3, 140.8, 140.0, 135.8, 135.5,
reaction mixture was extracted with ethyl acetate. The 131.3, 130.2, 130.0, 129.5, 128.7, 126.9, 125.7, 125.2, 123.7,
combined organic layer was washed with brine, dried over 120.1, 107.3, 68.6, 45.0, 38.0, 35.4, 34.6, 33.6, 26.9, 26.1, 24.5,
anhydrous Na2SO4, and evaporated under reduced pressure. 20.9. HRMS (TOF MS ES+): m/z calcd for C41H37N3O2S2 [M+H]+
The crude product compound 4a-d was used in Suzuki coupling 667.2327, found 667.2333.
without further purification.
Optical and electrochemical measurements
General synthesis of CS-25-28: The mixture of crude
compound 4a-d (0.5 mmol), 2 M K2CO3 (4 ml), compound 5
(0.19g, 0.497 mmol), Pd(PPh3)4 (0.06 mg, 0.050 mmol), and 1,4-
dioxane (30 mL) was refluxed for 24 h under Ar. After cooling,
water was added and the reaction mixture was extracted by
DCM. The combined organic layer was washed with brine, dried
over anhydrous Na2SO4, and evaporated under reduced
pressure. The crude product was dissolved in DCM (10ml) and
CF3COOH (2 mL) was added at r.t. The mixture was stirred at for
3 h and then evaporated under reduced pressure. The crude
product was purified by column chromatography
(DCM/MeOH=100:1) to yield CS-25-28 as a red solid.
Characterization of CS-25: 1H NMR (500 MHz, d6-DMSO,
ppm): δ 13.03 (s, 1H), 8.01-8.19 (m, 6H), 8.00 (d, J = 9.0 Hz, 1H),
7.53 (s, 1H), 7.48 (d, J = 4.0 Hz, 1H), 7.42 (d, J = 10.0 Hz, 1H),
7.19-7.24 (m, 4H), 6.88 (d, J = 10.0 Hz, 1H), 4.88-4.93 (m, 1H),
3.85-3.89 (m, 1H), 2.30 (s, 3H), 2.03-2.14 (m, 1H), 1.73-1.86 (m,
3H), 1.61-1.67 (m, 1H), 1.38-1.46 (m, 1H). 13C NMR (125 MHz,
d6-DMSO, ppm): δ 167.9, 153.5, 152.3, 147.9, 147.4, 141.2,
139.9, 136.2, 135.5, 131.4, 130.3, 130.2, 130.0, 129.7, 129.5,
126.9, 125.6, 125.1, 124.2, 122.5, 122.4, 120.2, 107.6, 68.8,
45.0, 35.3, 33.6, 24.5, 20.9. HRMS (TOF MS ES+): m/z calcd for
C35H27N3O2S2 [M+H]+ 585.1545, found 585.1548.
Characterization of CS-26: 1H NMR (500 MHz, d6-DMSO,
ppm): δ 13.08 (s, 1H), 8.09-8.18 (m, 6H), 8.02 (d, J = 9.0 Hz, 1H),
7.34 (s, 1H), 7.19-7.25 (m, 5H), 6.93 (d, J = 10.0 Hz, 1H), 4.89-
4.93 (m, 1H), 3.87-3.93 (m, 1H), 2.40 (s, 3H), 2.30 (s, 3H), 2.05-
2.12 (m, 1H), 1.77-1.85 (m, 3H), 1.63-1.70 (m, 1H), 1.41-1.46 (m,
1H). 13C NMR (125 MHz, d6-DMSO, ppm): δ 167.2, 153.5, 152.3,
147.5, 141.3, 140.0, 135.8, 134.4, 132.8, 132.6, 131.3, 130.6,
130.3, 130.2, 129.9, 129.6, 129.5, 128.2, 126.8, 125.1, 124.0,
120.2, 107.4, 68.8, 45.1, 35.4, 33.6, 24.5, 20.9, 15.7. HRMS (TOF
MS ES+): m/z calcd for C36H29N3O2S2 [M+H]+ 599.1701, found
599.1709.
Characterization of CS-27: 1H NMR (500 MHz, d6-DMSO,
ppm): δ 13.08 (s, 1H), 8.11-8.18 (m, 6H), 7.99 (d, J = 9.0 Hz, 1H),
7.18-7.29 (m, 6H), 6.94 (d, J = 10.0 Hz, 1H), 4.88-4.92 (m, 1H),
3.86-3.90 (m, 1H), 2.72-2.78 (m, 2H), 2.31 (s, 3H), 2.06-2.11 (m,
1H), 1.77-1.84 (m, 3H), 1.63-1.67 (m, 1H), 1.39-1.49 (m, 1H),
1.30 (t, J = 7.5 Hz, 3H). 13C NMR (125 MHz, d6-DMSO, ppm): δ
UV-visible spectra of four dyes both in solution and on TiO2
electrode were recorded by
a
Shimadzu UV-2501PC
spectrometer. The photoluminescence was measured on
Hitachi F-4600 spectrometer. The time-correlated PL signals of
all four dyes both in solution and on electrode were recorded
by FLS980 Spectrometer (Edinburgh Instrument). The PL decay
signals were detected at 680 nm upon excitation with
picosecond pulsed diode laser EPL-450 at 450 nm. The cyclic
voltammograms tests were performed on
a CHI660B
electrochemical workstation (CH Instruments) using a three-
electrode cell. A dye-loaded TiO2 electrode was used as the
working electrode and a Pt wire was used as the counter
electrode with a SCE reference electrode, while 0.1 M
tetrabutylammonium hexafluorophosphoric was used as the
supporting electrolyte. After the measurement, ferrocene was
added as the external reference for calibration (0.63 V vs NHE).
Fabrication and measurements of cell devices
For fabrication of DSSCs based on CS-25-28,
6 μm
nanocrystalline TiO2 electrodes with a 4 μm scattering layer
were used as the TiO2 electrodes. All the TiO2 electrodes were
prepared and modified according to the reported procedure.20
The dye-loaded electrodes were prepared by immersing TiO2
electrodes into around 0.3 mM dye solution (CHCl3/MeOH, v/v,
1/4) overnight. The active area was controlled to be 0.16 mm2.
H2PtCl6 solution (0.02 M in 2-propanol solution) was used to
prepare the counter electrode. The Pt catalyst was deposited on
the cleaned FTO glass through coating with a drop of H2PtCl6
solution with heat treatment at 500 ºC for 30 min. In this work,
a mixture of 0.5 M 1-butyl-3-methylimidiazolium iodide, 0.10 M
LiI, 0.05 M I2, and 0.5 M tert-butylpyridine in acetonitrile was
used as the redox electrolyte. The dye-loaded amount was
determined by desorbing the dye from the surface of dye-
sensitized TiO2 electrode (thickness: 6 μm, area: 2 × 2 cm2) into
NaOH solution (H2O/EtOH = 1/1, v/v) and analyzed by a UV-
visible spectrometer. The corresponding dye solution with
known concentration was also analyzed and used as external
standard. For dummy cell, 3 μm ZrO2 electrode was prepared by
exactly same method as described above, except using ZrO2
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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