D. Yu et al. / Tetrahedron xxx (2016) 1e7
3
on the photosensitive layer in vacuum and used as top electrodes.
The currentevoltage (IeV) characterization of the devices was car-
ried out on a computer-controlled Keithley source measurement
system. A solar simulator was used as the light source and the light
intensity was monitored by a standard Si solar cell. The active area
was 1ꢂ10ꢀ2 cm2 for each cell. The thicknesses of the spun-cast films
were recorded by a profilometer (Alpha-Step 200, Tencor In-
struments). The external quantum efficiency (EQE) was measured
with a Stanford Research Systems model SR830 DSP lock-in ampli-
fier coupled with WDG3 monochromator and a 150 W xenon lamp.
chromatography with PE as the eluent to obtain 5 as a white solid
(0.48 g, 83.6%). 1H NMR (400 MHz, CDCl3, TMS),
(ppm): 8.50 (d,
d
J¼9.3 Hz, 1H), 8.21e8.01 (m, 8H), 7.53 (d, J¼4.9 Hz, 1H), 7.39 (d,
J¼2.8 Hz, 1H), 7.27 (m, 1H).
2.3.5. 2-Bromo-5-(pyren-1-yl)thiophene (M5). To
a solution of
compound 5 (0.43 g, 1.5 mmol) in tetrahydrofuran (THF, 30 mL) was
added N-bromosuccinimide (NBS, 0.28 g, 1.57 mmol) in a two-neck
round flask. The mixture was then stirred for 2.5 h at rt. After the
solvent was distilled off, the residue was purified by silica gel col-
umn chromatography using PE as eluent to obtain M5 as a yellow
2.3. Synthesis of SMs
solid (0.45 g, 82.7%). 1H NMR (400 MHz, CDCl3, TMS),
d (ppm): 8.46
(d, J¼8.0 Hz, 1H), 8.03e8.23 (m, 8H), 7.22 (d, J¼6.8 Hz, 1H), 7.13 (d,
2.3.1. (E)-6,6ʹ-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)iso-
indigo (M2). Compound (E)-6,6ʹ-dibromoisoindigo (M1, 0.94 g,
1.08 mmol), bis(pinacolato)di-boron (1, 0.55 g, 2.16 mmol), potas-
sium acetate (KOAc, 0.85 g, 8.84 mmol) and [1,10-
bis(diphenylphosphino)-ferrocene]dichloroplladium (Pd(dppf)Cl2,
0.15 g, 0.22 mmol) were mixed with 30 mL dry 1,4-dioxane, and
heated to reflux for 24 h under the nitrogen atmosphere. After
quenched with distilled water (50 mL), the mixture was extracted
with dichloromethane (DCM, 20 mLꢂ3). The combined organic
layer was dried over anhydrous magnesium sulfate (MgSO4) and
filtered. The solvent was removed off by rotary evaporation and the
residue was purified by silica gel column chromatography with
petroleum ether (PE)-DCM (v/v, 2/1) as the eluent to obtain M2 as
J¼6.5 Hz, 1H).
2.3.6. Synthesis of IID(Py)2. To a mixture of M2 (0.32 g, 0.33 mmol),
M3 (0.37 g, 1.32 mmol) and Pd(PPh3)4 (0.02 g, 0.017 mmol) was
added a degassed mixture of toluene (30 mL), anhydrous ethanol
(15 mL) and 2 M potassium carbonate aqueous solution (3.0 mL).
The mixture was refluxed for 24 h under nitrogen atmosphere.
After cooled to RT, the mixture was extracted with DCM (30 mLꢂ3)
and the combined organic layer was dried over MgSO4. The solvent
was removed off by rotary evaporation and the residue was purified
by silica gel column chromatography with PE-DCM (v/v, 2/1) as the
eluent to obtain ID(Py)2 as a black solid (0.25 g, 68.8%). 1H NMR
(400 MHz, CDCl3, TMS),
d
(ppm): 9.42 (d, J¼8.0 Hz, 2H), 8.33 (d,
a red solid (0.50 g, 50.4%). 1H NMR (400 MHz, CDCl3, TMS),
d
(ppm):
J¼9.1 Hz, 2H), 8.28e8.05 (m,16H), 7.39 (d, J¼8.0 Hz, 2H), 7.11 (s, 2H),
3.78 (d, J¼6.5 Hz, 4H), 2.03 (m, 2H), 1.39e1.19 (m, 48H), 0.79 (d,
J¼7.7 Hz, 12H). 13C NMR (400 MHz, CDCl3, TMS), (ppm): 168.82,
145.56, 145.49, 137.15, 133.04, 131.54, 131.10, 131.01, 129.82, 129.81,
128.51, 127.86, 127.82, 127.40, 127.12, 126.18, 125.41, 125.11, 124.94,
124.75, 124.60, 120.94, 110.59, 110.57, 44.87, 44.86, 36.43, 31.85,
31.83, 31.78, 30.04, 29.71, 29.57, 29.28, 26.58, 26.54, 22.64, 22.62,
14.07, 14.03. MALDI-TOF MS (m/z) for C80H90N2O2, calcd: 1111.58,
Found, 1111.73. Anal. calcd for: C80H90N2O2: C, 86.44; H, 8.16; N,
2.52. Found: C, 86.21; H, 8.05; N, 2.48.
9.13 (d, J¼7.7 Hz, 2H), 7.47 (d, J¼7.8 Hz, 2H), 7.16 (s, 2H), 3.69 (d,
J¼6.8 Hz, 4H), 1.95 (m, 2H), 1.36 (s, 24H), 1.25 (m, 48H), 0.86 (m,
12H). MALDI-TOF MS (m/z) for C60H96B2N2O6, calcd: 963.87, Found,
963.75.
2.3.2. Trimethyl(2-(pyren-1-yl)ethynyl)silane (3). Compound 1-
bromopyrene (M3, 0.56 g, 2.00 mmol), ethynyltrimethylsilane (2,
0.24 g, 2.40 mmol), dichlorobis(triphenylphosphine)palladium(II)
(Pd(PPh3)2Cl2, 0.17 g, 0.24 mmol), cuprous iodide (CuI, 0.02 g,
0.11 mmol) were mixed with 30 mL dry triethylamine, and heated
to reflux for 24 h under the nitrogen atmosphere. After quenched
with distilled water (50 mL), the mixture was extracted with DCM
(30 mLꢂ3). The combined organic layer was dried over anhydrous
MgSO4 and filtered. The solvent was removed off by rotary evapo-
ration and the residue was purified by silica gel column chroma-
tography with PE as the eluent to obtain 3 as a yellow solid (0.57 g,
2.3.7. Synthesis of IID(AcePy)2. To a mixture of M1 (0.15 g,
0.17 mmol), M4 (0.14 g, 0.66 mmol), Pd(PPh3)2Cl2 (0.02 g,
0.028 mmol), CuI (0.01 g, 0.056 mmol) was added a degassed
mixture of triethylamine (30 mL). The mixture was refluxed for 24 h
under nitrogen atmosphere. After cooled to RT, the mixture was
extracted with DCM (30 mLꢂ3) and the combined organic layer
was dried over MgSO4. The solvent was removed off by rotary
evaporation and the residue was purified by silica gel column
chromatography with PE-DCM (v/v, 2/1) as the eluent to obtain
ID(AcePy)2 as a black solid (0.13 g, 68.0%). 1H NMR (400 MHz,
95.0%). 1H NMR (400 MHz, CDCl3, TMS),
1H), 8.25e8.02 (m, 8H), 0.40 (s, 12H).
d
(ppm): 8.58 (d, J¼9.1 Hz,
2.3.3. 1-Ethynylpyrene (M4). Compound 3 (0.50 g, 1.67 mmol), so-
dium hydroxide (NaOH, 0.02 g, 0.50 mmol) were mixed with
methanol (20 mL) and THF (20 mL), and stirred for 6 h at rt. After
quenched with distilled water (50 mL). Then, the mixture was
extracted with DCM (20 mLꢂ3). The combined organic layer was
dried over anhydrous MgSO4 and filtered. The solvent was removed
off by rotary evaporation and the residue was purified by silica gel
column chromatography with PE as the eluent to obtain M4 as
a gray solid (0.57 g, 95.0%). 1H NMR (400 MHz, CDCl3, TMS),
CDCl3, TMS),
d
(ppm): 9.27 (d, J¼8.0 Hz, 2H), 8.68 (d, J¼12.0 Hz, 2H),
8.25e8.04 (m, 16H), 7.41 (d, J¼8.0 Hz, 2H), 7.07 (s, 2H), 3.77 (d,
J¼6.8 Hz, 4H), 2.04 (m, 2H), 1.41e1.24 (m, 48H), 0.87e0.83 (m, 12H).
13C NMR (400 MHz, CDCl3, TMS), (ppm): 168.30, 145.19, 132.58,
132.09, 131.63, 131.26, 131.06, 129.81, 128.55, 128.43, 127.23, 127.08,
127.07, 126.29, 125.79, 125.75, 125.66, 125.38, 124.56, 124.51, 124.30,
121.85, 117.33, 110.59, 96.13, 92.17, 44.67, 44.66, 36.33, 31.91, 31.89,
31.73, 30.11, 29.75, 29.64, 29.36, 26.57, 26.54, 22.68, 22.67, 14.10,
14.08. MALDI-TOF MS (m/z) for C84H90N2O2, calcd: 1159.63, Found,
1160.25. Anal. calcd for: C84H90N2O2: C, 87.00; H, 7.82; N, 2.42.
Found: C, 86.68; H, 7.52; N, 2.08.
d
(ppm): 8.60 (d, J¼9.1 Hz, 1H), 8.31e7.98 (m, 8H), 3.64 (s, 1H).
2.3.4. 2-(Pyren-1-yl)thiophene (5). Compound M3 (0.56 g,
2.00 mmol), 2-tributyl(thiophen-2-yl)stannane (4, 1.12 g,
3.00 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4,
0.20 g, 0.17 mmol) were mixed with 100 mL toluene, and heated to
reflux for 24 h under the nitrogen atmosphere. After quenched with
distilled water (50 mL), the mixture was extracted with DCM
(30 mLꢂ3). The combined organic layer was dried over anhydrous
MgSO4 and filtered. The solvent was removed off by rotary evapo-
ration and the residue was purified by silica gel column
2.3.8. Synthesis of IID(ThePy)2. To a mixture of M3 (0.16 g,
0.17 mmol), M5 (0.19 g, 0.66 mmol) and Pd(PPh3)4 (0.02 g,
0.017 mmol) was added a degassed mixture of toluene (30 mL),
anhydrous ethanol (15 mL) and 2 M potassium carbonate aqueous
solution (2 mL). The mixture was refluxed for 24 h under nitrogen
atmosphere. After cooled to RT, the mixture was extracted with
DCM (30 mLꢂ3) and the combined organic layer was dried over