L.S. Chinelatto Jr et al. / Journal of Photochemistry and Photobiology A: Chemistry 210 (2010) 130–139
133
Fig. 3. Synthesis of PF(o)n and OF(mb)n.
0.40–0.37 (m, 12H). 13C RMN (100 MHz, CDCl3): ı (ppm) 151.2,
151.1, 150.8, 141.9 141.0, 140.3, 140.2, 139.5, 128.7 127.1, 126.8,
126.5, 126.1 126.0, 123.9, 123.0 119.9, 119.7, 55.1, 54.7, 48.0, 44.2,
34.7, 34.3, 31.3, 30.5, 28.3, 27.3, 22.7, 21.1, 14.0, 11.0, 10.4. Elem.
Anal. Calcd for C75H98: C, 90.12; H, 9,88. Found: C, 89.60; H, 10.04.
EM (MALDI-TOF, dithranol) m/z (%):770.6 (100), 998.7 (80 [M]+);
MM calcd: 998.77.
RMN (400 MHz, CDCl3): ı (ppm) 7.92–7.74 (m, 6H), 7.74–7.58 (m,
8H), 7.47–7.28 (m, 6H), 2.28–1.91 (m, 12H), 1.38–1.06 (m, 35H),
1.06–0.51 (m, 55H). 13C RMN (100 MHz, CDCl3): ı (ppm) 151.3,
151.2, 151.0, 140.8, 140.8, 140.7, 140.2, 140.0, 128.7, 127.1, 126.9,
126.2, 125.9, 125.8, 122.9, 121.4, 119.8, 119.7, 55.1, 55.0, 40.4, 40.3,
34.7, 33.9, 31.8, 30.1, 29.2, 28.2, 28.2, 27.3, 23.8, 22.7, 22.6, 14.0,
10.5, 10.4. Elem. Anal. Calcd for C87H122: C, 89.50; H, 10.50. Found:
C, 89.20; H, 10.80. EM (MALDI-TOF, dithranol) m/z (%): 1166.9 (100
[M]+); MM calcd: 1166.95.
2.2.2. General polymerization procedure and characterization
data for PF(o)n and OF(mb)n
The procedure is gathered in Fig. 3. A Schlenk was charged
with Ni(COD)2 (2.146 mmol) and 2,2ꢀ-bipyridine (2.145 mmol) in
a glove box and then purged with argon. DMF (8 mL) and COD
(2.146 mmol) were added and the solution subsequently heated
at 70 ◦C for 30 min. Finally, the 2,7-dibromofluorene (1.823 mmol)
dissolved in toluene (8 mL) was added and the reaction vigorously
stirred at 70 ◦C for 24 h. The polymer was isolated from the reaction
crude by flash column chromatography over silica gel using hexane
as eluant.
2.2.1.5. Characterization data for OF(o)4(eh)1. The product was
obtained by Suzuki coupling of 7-bromo-9,9,9ꢀ,9ꢀ-tetrakis(n-
octyl)-2,2ꢀ-bifluorene (5) and 9,9-bis(2-ethylhexyl)fluoren-2,7-
diyl-boronic acid (6). It was purified by MPLC using hexane as eluant
and gradually increasing polarity with dichloromethane. The tar-
get compound was isolated as a white solid in 71% yield. IR (KBr,
cm−1) ꢂ: 1608, 1456 (Ar, C–C); 815 (Ar). 1H RMN (400 MHz, CDCl3):
ı (ppm) 7.90–7.40 (m, 10H), 7.40–7.57 (m, 16H), 7.43–7.30 (m, 6H),
2.25–1.93 (m, 20H), 1.34–1.03 (m, 84H), 1.03–0.52 (m, 66H). 13C
RMN (100 MHz, CDCl3): ı (ppm) 151.8, 151.7, 151.5. 151.4, 151.3,
140.9, 140.7, 140.2, 140.0, 139.8, 128.8, 127.2, 127.1, 126.9, 126.3,
126.0, 125.9, 123.0, 121.5, 121.4, 121.3, 119.9, 119.6, 119.6, 55.3,
55.2, 55.1, 40.4, 40.3, 34.8, 34.0, 34.0, 31.8, 30.0, 29.2, 28.2, 28.2,
27.3, 27.1, 23.9, 23.8, 22.8, 22.8, 22.6, 14.1, 10.5, 10,5, 10.4. Elem.
Anal. Calcd for C145H202: C, 89.53; H, 10.47. Found: C, 89.35; H,
10.70. EM (MALDI-TOF, dithranol) m/z (%): 1944.3 (100 [M+1]+);
MM calcd: 1943.58.
2.2.2.1. Characterization data for PF(o)n. The polymer was isolated
as a yellow powder in 48% yield. GPC (THF, polystyrene stan-
dards): Mw 19,046, Mn 12,763, polydispersity 1.5. IR (KBr, cm−1
)
ꢂ: 3019 (Ar–H), 2988 (C–H), 1609, 1457 (ArC–C), 813 (Ar). 1H NMR
(400 MHz, CDCl3) ı (ppm): 7.84 (d, J = 8.1 Hz, 2H,), 7.74–7.60 (m,
4H), 2.21–1.96 (m, 4H), 1.25–1.03 (m, 20H), 0.91–0.60 (m, 10H).
13C RMN (100 MHz, CDCl3): ı (ppm) 151.82, 140.52, 140.00, 126.15,
121.53, 120.04, 55.34, 40.49, 31.87, 30.08, 29.26, 23.95, 22.62, 14.10.
Elem. Anal. Calcd for C29H40: C, 89.61; H, 10.39. Found: C, 89.45; H,
10.55.
2.2.1.6. Characterization data for OF(mb)2(o)1. The product
was obtained by Suzuki coupling of 2-bromo-9,9-bis[(S)-2-
methylbutil]fluorene (2) and 9,9-bis(n-octyl)fluoren-2,7-diyl-
bis(trimetilen)borate (7). It was purified by MPLC using hexane as
eluant and gradually increasing polarity with dichloromethane.
The target compound was isolated as a viscous colourless liquid
in 67% yield. IR (KBr, cm−1) ꢂ: 1611, 1507 (Ar, C–C); 814 (Ar). 1H
RMN (400 MHz, CDCl3): ı (ppm) 7.93–7.67 (m, 14H), 7.57–7.35 (m,
6H), 2.36–1.96 (m, 12H), 1.34–1.15 (m, 28H), 1.04–0.67 (m, 26H),
0.43–0.38 (m, 12H). 13C RMN (100 MHz, CDCl3): ı (ppm) 151.8,
151.3, 150.9, 141.7, 140.9, 140.6, 140.4, 140.1, 128.8, 127.2, 126.6,
126.8, 126.1, 123.9, 122.5, 121.6, 119.9, 119.7, 54.8, 48.0, 47.7, 40.2,
31.8, 31.2, 31.2, 30.0, 30.6, 29.2, 29.2, 22.6, 21.2, 14.1, 11.0. Elem.
Anal. Calcd for C75H98: C, 90.12; H, 9.88. Found: C, 89.38; H, 10.11.
EM (MALDI-TOF, dithranol) m/z (%): 770.7 (100), 998.8 (80 [M]+);
MM calcd: 998.77.
2.2.2.2. Characterization data for OF(mb)n. The compounds were
isolated as a white powder in 69% yield. GPC (THF, polystyrene stan-
dards): Mw 7725, Mn 4798, polydispersity 1.6. IR (KBr, cm−1) ꢂ:
3024 (Ar–H); 2961, 2929 (C–H), 1611, 1460 (ArC–C), 814, 740 (Ar).
1H NMR (400 MHz, CDCl3) ı (ppm): 7.95–7.79 (m, 2H), 7.79–7.60
(m, 4H), 2.37–2.15 (m, 2H), 2.07–1.88 (m, 2H), 1.09–0.78 (m, 6H),
0.76–0.59 (m, 6H), 0.47–0.22 (m, 6H). 13C RMN (100 MHz, CDCl3): ı
(ppm) 151.50, 140.20, 130.12, 127.13, 122.75, 121.24, 54.99, 47.67,
31.28, 21.66, 20.98, 11.93. Elem. Anal. Calcd for C23H28: C, 90.71; H,
9.29. Found: C, 90.27; H, 9.73.
2.3. Preparation of films
Thin films of polymers PF(o)n and OF(mb)n were deposited on
from 0.5 mL of a solution of the polymer in THF (1 g/L).
Films of oligofluorenes were prepared by in situ photopolymer-
ization of reactive nematic blends that contained a non-emissive
liquid crystalline matrix and the oligofluorene in 95:5 molar
ratio [5–7,25]. The liquid crystalline matrix contained 1,2-di[4-
2.2.1.7. Characterization data for OF(mb)2(eh)1. The product
was obtained by Suzuki coupling of 2-bromo-9,9-bis[(S)-2-
methylbutil]fluorene (2) and 9,9-bis(2-ethylhexyl)fluoren-2,7-
diyl-boronic acid (6). It was purified by MPLC using hexane as
eluant and gradually increasing polarity with dichloromethane.
The target compound was isolated as a viscous colourless liquid
in 59% yield. IR (KBr, cm−1) ꢂ: 1607, 1508 (Ar, C–C); 818 (Ar). 1H
RMN (400 MHz, CDCl3): ı (ppm) 7.88–7.70 (m, 14H), 7.55–7.34 (m,
6H), 2.38–1.96 (m, 12H), 1.10–0.84 (m, 24H), 0.83–0.61 (m, 30H),
(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene
and 1-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methyl-4-(4-
octylbenzoyloxy)benzene (C6Mm) in 10:85 molar ratio. C6M
(C6M)