76
M. Luo et al. / Dyes and Pigments 101 (2014) 74e84
120
100
80
60
40
20
0
2 M K2CO3 aqueous solution (9 mL) and TBAB (0.01 g) were
P5
added. The mixture was stirred for 30 min under an argon at-
mosphere at room temperature. Then the Pd(PPh3)4 catalyst was
added and the reaction mixture was stirred at 80 ꢀC for 24 h.
After cooling to room temperature, the product was concentrated
and purified by silica gel column chromatography with CH2Cl2/n-
hexane mixed solvent (1:2 by volume) to afford a pale yellow
powder P4NH2 (3.16 g, yield 91.2%). 1H NMR (300 MHz, CDCl3)
(a)
0%
10%
50%
60%
70%
80%
90%
d
(ppm): 6.41e6.46 (d, J ¼ 7.8 Hz, 2 H); 6.76e6.83 (d, J ¼ 7.8 Hz,
2 H); 6.94e7.18 (m, 17 H). MS (EI) calcd for C26H21N 347, found
347. Anal. calcd for C26H21N: C 89.88, H 6.09, N 4.03; Found: C
89.84, H 6.05, N 4.07.
2.3. Synthesis of 3,4,5-tris(dodecyloxy)-N-(4-(1,2,2-triphenylvinyl)
phenyl)benzamide (P4)
400
450
500
550
600
650
700
Wavelength / nm
110
100
90
80
70
60
50
40
30
20
10
0
To P4NH2 (0.18 g, 0.52 mmol) and 3 (0.42 g, 6 mmol) in THF
(50 mL), DMAP (0.01 g) and EDC-HCl (0.01 g) were added. The
mixture was stirred for 3 days under an argon atmosphere at room
temperature. Excess ethanol was added and the resulting precip-
itate was collected. Then crystallized from THF and ethanol
mixture for 3 times to obtain P4 as a white solid (0.48 g, yield
92.8%). Melting point: w78 ꢀC (DSC). 1H NMR (300 MHz, CDCl3)
(b)
P4
P5
d
(ppm): 0.89 (t, J ¼ 6.3 Hz, 9 H), 1.20e1.48 (m, 52 H), 1.68e1.93
(m, 8 H), 3.96e4.07 (m, 6 H), 6.96e7.17 (m, 19 H), 7.36 (d,
J ¼ 8.4 Hz, 2 H), 7.59 (s, 1 H). 13C NMR (CDCl3, 75 MHz)
d (ppm):
165.6, 153.3, 143.8, 141.5, 141.0, 140.4, 140.1, 136.4, 131.5, 130.1,
127.8, 126.7, 126.6, 119.3, 105.8, 73.8, 69.7, 32.3, 30.1,29.7, 26.5, 23.1,
14.5. FT-IR (KBr)
y
(cmꢁ1): 3306, 2921, 2849, 1640, 1580, 1527,
1497, 1467, 1335, 1233, 1113, 748, 699. MS (EI), m/z: 1004 ([M]þ,
calcd for C69H97NO4, 1004). Anal. calcd for C69H97NO4: C 82.50, H
9.73, N 1.39; Found: C 82.44, H 9.81, N 1.32.
-10
0
20
40
60
80
100
VH O
%
Fig. 1. (a) PL spectra of P5 in THF/water mixtures with different water fractions (inset:
the images of P5 were taken at room temperature under 365 nm UV light in THF and
90% water); (b) Change in PL peak intensities of P4 and P5 with different water
2.4. Synthesis of P5NH2
TPE-Br (2.50 g, 6.08 mmol) and 4-aminophenylboronic acid
(1.65 g, 12 mmol) were dissolved in the pure THF (50 mL), then
TBAB (0.01 g) and K2CO3 (2 M, aq. soln., 9 mL) were added. The
mixture was stirred at room temperature for 0.5 h under argon gas
followed by addition of the Pd(PPh3)4 catalyst and then heated to
80 ꢀC for 24 h. The reaction mixture was concentrated and purified
by column chromatography on a silica gel column with CH2Cl2/n-
hexane (1:1 by volume) as eluent to give light yellow crystalline
powder P5NH2 (2.35 g, 92.5% yield). 1H NMR (300 MHz, DMSO-d6)
fractions in THF/water mixtures (concentration 10 mM, excitation wavelength 365 nm).
pellet at 1500 psi for 5 min. Annealing experiments were done on a
hot-stage with automatic temperature control system for 5 min, the
annealing temperature was 70 ꢀC. The experiment of solvent vapor
fuming treatment was performed by filling the pressed sample on a
grooved glass slide, which was then placed in a large beaker satu-
rated with CH2Cl2 vapor for 5 min at room temperature.
2.2. Synthesis of 4-(1, 2, 2-triphenylvinyl)benzenamine (P4NH2)
d
(ppm): 5.14e5.24 (s, 2 H); 6.54e6.62 (d, J ¼ 8.4 Hz, 2 H); 6.88e
7.36 (m, 21 H). MS (EI) calcd for C32H25N 423, found 423. Anal.
calcd for C32H25N: C 90.74, H 5.95, N 3.31; Found: C 90.71, H 5.92,
N 3.35.
To 2-bromo-1,1,2-triphenylethylene (3.35 g, 10 mmol) and 4-
aminophenylboronic acid 1.65 g (12 mmol) in THF (50 mL),
Fig. 2. (A) SEM images of THF/water (10/90, v/v) mixture of P5, (B) SEM image of xerogel formed with P5 in ethanol.