poured on iced water (100 mL) and extracted with dichloromethane.
The combined organic fractions were washed with brine (100 mL), dried
over MgSO4, filtered and concentrated in vacuo. The crude product was
purified by chromatography using petroleum ether/dichloromethane
(3:1 v/v) as eluent to obtain a yellow oil in the yield of 65% (3.4 g). H
NMR (300 MHz, CDCl3) δ (ppm): 7.83−7.1 (m, 2H), 7.66-7.61 (m, 2H),
7.47-7.36 (m, 5H).
oTPE-pTPE: White powder. Yield: 48%. 1H NMR (300 MHz, CDCl3)
δ (ppm): 7.13-6.80 (m, 36H), 6.46-6.43 (m, 2H). 13C NMR (75 MHz,
CDCl3)
δ (ppm): 144.2, 143.4, 142.2, 141.1, 139.9, 138.9, 133.0,
131.6, 130.9, 130.7, 128.5, 128.0, 127.6, 127.2, 127.0, 126.7. MS (EI),
m/z: 662.40 ([M+], calcd. for C52H38: 662.86). HRMS: m/z for C52H38
[M+NH4+], calcd.: 680.3312; found: 680.3334.
1
oTPE-mTPE: White powder. Yield: 40%. 1H NMR (300 MHz, CDCl3)
δ (ppm): 7.08-6.88 (m, 33H), 6.81-6.78 (m, 2H), 6.64-6.61 (m, 3H). 13C
NMR (75 MHz, CDCl3) δ (ppm): 144.0, 141.2, 139.8, 137.5, 132.2, 131.6,
131.3, 130.3, 130.0, 129.1, 128.1, 127.9, 126.9, 126.7, 122.7. MS (EI),
m/z: 662.42 ([M+], calcd. for C52H38: 662.86). HRMS: m/z for C52H38
[M+NH4+], calcd.: 680.3312; found: 680.3319.
Synthesis of mTPE-Br: A 2.3 M solution of n-butyllithium in hexane
(4.09 mmol, 1.78 mL) was added to a solution of diphenylmethane
(0.86 g, 5.12 mmol) in anhydrous tetrahydrofuran (40 mL) at 0 °C
under an atmosphere of argon. After stirring for 1 h at this temperature,
3-bromobenzophenone (0.89 g, 3.41 mmol) was added. After 2 h, the
mixture was slowly warmed to room temperature. Then, the reaction
was quenched with an aqueous solution of ammonium chloride and
the mixture was extracted with dichloromethane. The organic layer was
evaporated after drying with anhydrous sodium sulfate, and the resulting
crude product was dissolved in toluene (25 mL). The p-toluenesulfonic
acid (0.12 g, 0.68 mmol) was added, and the mixture was refluxed
overnight and cooled to room temperature. The mixture was evaporated
and the crude product was purified by silica gel column chromatography
using petroleum ether as eluent to obtain a white powder in the yield
of 50% (0.7 g). 1H NMR (300 MHz, CDCl3) δ (ppm): 7.20-7.11 (m,
11H), 7.02-7.01 (m, 5H), 6.96-6.95 (m, 2H). 13C NMR (75 MHz, CDCl3)
δ (ppm): 146.0, 143.4, 143.3, 143.1, 142.2, 139.5, 134.2, 131.3, 130.1,
129.6, 129.3, 128.0, 127.8, 126.9, 126.8, 121.9. MS (EI), m/z: 412.13
([M+], calcd. for C26H19Br: 411.33).
Crystallographic data (excluding structure factors) for the structure(s)
reported in this paper have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication nos. CCDC-
894519 and 894520.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
Synthesis of oTPE-Br: Prepared according to a similar procedure
for mTPE-Br from Compound 2. White powder. Yield: 30%. 1H
NMR (300 MHz, CDCl3) δ (ppm): 7.17-7.03 (m, 19H). MS (EI), m/z:
412.10 ([M+], calcd. for C26H19Br: 411.33).
Z.L. is grateful to the National Science Foundation of China (no.
21161160556), the National Fundamental Key Research Program
(2011CB932702, 2013CB834700), and the Open Project of State Key
Laboratory of Supramolecular Structure and Materials (sklssm201219)
for financial support. D.M. is grateful to the Science Fund for Creative
Research Groups of NSFC (20921061), and the National Natural Science
Foundation of China (50973104, 60906020) for financial support.
Synthesis of Compound 3: A 2.3 M solution of n-butyllithium in
hexane (15.0 mmol, 6.5 mL) was added to a solution of mTPE-Br
(4.12 g, 10.0 mmol) in anhydrous tetrahydrofuran (60 mL) at –78 °C
under an atmosphere of argon. After stirring for 4 h, 2-isopropoxy-
4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.1 mL) was added. After 2 h,
the mixture was slowly warmed to room temperature. After stirring
overnight, the reaction was terminated by the added brine. The mixture
was extracted with dichloromethane, and the combined organic layer
was dried over anhydrous sodium sulfate. After filtration and solvent
evaporation, the crude product was purified by silica gel column
chromatography using petroleum ether/dichloromethane (5:1 v/v) as
eluent. White powder of 3 was obtained in the yield of 60% (2.30 g).
Received: September 12, 2012
Published online: December 4, 2012
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1H NMR (300 MHz, CDCl3)
δ (ppm): 7.53-7.48 (m, 2H),
7.09-7.02 (m, 17H), 1.28 (s, 12H). 13C NMR (75 MHz, CDCl3) δ (ppm):
143.6, 143.3, 142.9, 141.1, 140.8, 137.5, 134.2, 132.7, 131.3, 131.2,
127.5, 127.0, 126.3, 126.2, 83.6, 24.7. MS (EI), m/z: 458.35 ([M+], calcd
for C32H31BO2, 458.40).
General Procedure for the Synthesis of Compounds mTPE-pTPE, mTPE-
mTPE, oTPE-mTPE and oTPE-pTPE: mTPE-mTPE: A mixture of mTPE-Br
(412 mg, 1 mmol), compound 3 (459 mg, 1 mmol), Pd(PPh3)4 (0.10 g,
4% mmol), and potassium hydroxide (236 mg, 5 mmol) in 15 mL of
THF and 3 mL of distilled water in a 50 ml Schlenk tube was refluxed
for 2 d under argon. The mixture was extracted with dichloromethane.
The combined organic extracts were dried over anhydrous Na2SO4 and
concentrated by rotary evaporation. The crude product was purified by
column chromatography on silica gel using dichloromethane/petroleum
ether (1:5 v/v) as eluent to afford the product as a white powder in the
yield of 61.2% (320 mg). 1H NMR (300 MHz, CDCl3) δ (ppm): 7.09-7.04
(m, 32H), 6.97-6.92 (m, 6H). 13C NMR (75 MHz, CDCl3) δ (ppm): 144.0,
143.9, 143.7, 141.5, 141.2, 140.5, 131.6, 130.6, 130.2, 128.1, 127.9, 126.7,
125.4. MS (EI), m/z: 662.70 ([M+], calcd. for C52H38: 662.86). HRMS: m/z
for C52H38 [M+NH4+], calcd.: 680.3312; found: 680.3307.
mTPE-pTPE: White powder. Yield: 65%. 1H NMR (300 MHz, CDCl3) δ
(ppm): 7.09-6.98 (m, 38H). 13C NMR (75 MHz, CDCl3) δ (ppm): 144.2,
144.1, 143.9, 143.8, 142.8, 141.5, 141.3, 141.1, 140.8, 140.1, 139.1, 131.8,
131.6, 130.5, 130.4, 128.3, 128.0, 127.9, 126.7, 126.4, 125.3. MS (EI),
m/z: 662.79 ([M+], calcd. for C52H38: 662.86). HRMS: m/z for C52H38
[M+NH4+], calcd.: 680.3312; found: 680.3322.
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Adv. Funct. Mater. 2013, 23, 2329–2337