W. Huang, Q.-L. Fan, et al.
slowly warmed to room temperature. The mixture was stirred (vigorous
stirring was required to avoid gel formation) at room temperature for
three days and then was poured onto a mixture of crushed ice containing
sulfuric acid (5%) with stirring. The mixture was extracted with ether,
and the combined extracts were evaporated to give 9,9-dioctylfluorene-
2,7-diboronic acid. The crude acid was washed with hexane to give a
white solid (4.3 g, 45%). The diboronic acid was then refluxed with 1,3-
propanediol (1.2 g, 20 mmol) in toluene for 10 h. After working up, the
crude product was recrystallized from hexane to afford 9,9-dioctylfluor-
ene-2,7-bis-(trimethylene boronate) (3.6 g, 72%) as white crystals.
1H NMR (400 MHz, CDCl3): d=7.75 (d, J=8.4 Hz, 2H), 7.67–7.72 (m,
4H), 4.21 (t, 8H), 2.10 (m, 4H), 1.98 (m, 4H), 0.92–1.23 (m, 20H), 0.81
(t, J=7.2 Hz, 6H), 0.52 ppm (m, 4H); elemental analysis calcd (%) for
C35H52B2O4: C 75.28, H 9.39; found: C 75.45, H 9.75.
of Ir complex), 8.30 (m, 11%4H; ArH of Ir complex), 7.10 (m, 11%
2H; ArH of Ir complex), 6.86 ppm (m, 11%2H; ArH of Ir complex);
13C NMR (100 MHz, CDCl3): d=152.04, 140.72, 140.24, 129.03, 127.44,
126.39, 121.72, 120.21, 55.57, 40.63, 32.04, 31.20, 30.27, 29.46, 24.14, 22.85,
14.32 ppm; elemental analysis calcd (%): C 82.47, H 9.10, N 1.20; found:
C 79.37, H 8.86, N 1.24. According to the NMR data, the Ir complex con-
tent in the copolymer was around 11%.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China under Grants 60325412, 90406021, 50428303, and
20504007 as well as the Shanghai Commission of Science and Technology
under Grants 03DZ11016, and 04XD14002, and the Shanghai Commis-
sion of Education under Grant 2003SG03.
General procedure for the copolymerization of fluorene and Ir complex
by the Suzuki cross coupling method: To a mixture of 9,9-dioctylfluor-
ene-2,7-bis(trimethylene boronate) (1 equiv), dibromo compound
(1 equiv), including the Ir complex and 9,9-dioctyl-2,7-dibromofluorene,
tetrabutylammonium bromide, and 4.0 mol% [PdCAHTRE(UGN PPh3)4], was added a
degassed mixture of toluene ([monomer]=0.25m) and aqueous 2m potas-
sium carbonate (3:2 in volume). The mixture was vigorously stirred at
85–908C for 72 h and then bromobenzene was added. After the mixture
was cooled to room temperature, it was washed with water. The solution
was concentrated and then it was slowly add dropwise to a mixture of
methanol and deionized water (220 mL, 10:1 v/v). A fibrous solid was ob-
tained by filtration. The solid was dissolved in THF and then the solution
was evaporated. The concentrated solution obtained was dropped slowly
into methanol (250 mL) again. And this procedure was repeated twice in
acetone in place of methanol. The fibrous solid was filtered and was then
washed with acetone in a Soxhlet apparatus for 3–5 days to remove
oligomers and catalyst residues. The resulting polymers were collected
and dried under vacuum. Yields: 55–70%.
PFO: 1H NMR (400 MHz, CDCl3): d=7.66–7.86 (m, 6H), 2.12 (m, 4H),
1.05–1.28 (m, 20H), 0.63–0.89 ppm (m, 10H); 13C NMR (100 MHz,
CDCl3): d=151.81, 140.68, 140.02, 126.18, 121.49, 120.22, 55.34, 40.43,
31.93, 30.88, 30.08, 29.37, 24.12, 22.64, 14.28 ppm; elemental analysis
calcd (%): C 89.62, H 10.38; found: C 88.86, H 10.07.
PFO-Ir05: 1H NMR (400 MHz, CDCl3): d=7.67–7.85 (m, 6H), 2.12 (m,
4H), 1.05–1.28 (m, 20H), 0.63–0.89 ppm (m, 10H); 13C NMR (100 MHz,
CDCl3): d=152.04, 140.72, 140.26, 126.39, 121.72, 120.21, 55.57, 40.62,
32.03, 30.28, 30.18, 29.46, 24.14, 22.84, 14.31 ppm; elemental analysis
calcd (%): C 87.96, H 10.22, N 0.07; found: C 84.52, H 9.73, N 0.21.
PFO-Ir2: 1H NMR (400 MHz, CDCl3): d=7.67–7.85 (m, 6H), 2.12 (m,
4H), 1.05–1.28 (m, 20H), 0.63–0.89 ppm (m, 10H); 13C NMR (100 MHz,
CDCl3): d=151.81, 140.50, 140.02, 128.79, 127.21, 126.17, 121.49, 119.98,
55.34, 40.38, 31.80, 30.96, 30.04, 29.23, 23.92, 22.61, 14.08 ppm; elemental
analysis calcd (%): C 88.05, H 10.03, N 0.27; found: C 86.61, H 10.03, N
0.23.
[1]a) M. A. Baldo, D. F. OꢁBrien, Y. You, A. Shoustikov, S. Sibley,
M. E. Thompson, S. R. Forrest, Nature 1998, 395, 151–154; b) S. La-
mansky, R. C. Kwong, M. Nugent, P. I. Djurovich, M. E. Thompson,
Org. Electron. 2001, 2, 53–62; c) X. Gong, M. R. Robinson, J. C. Os-
trowski, D. Moses, G. C. Bazan, A. J. Heeger, Adv. Mater. 2002, 14,
581–585.
[2]a) E. Holder, B. M. W. Langeveld, U. S. Schubert. Adv. Mater. 2005,
17, 1109–1121; b) T. D. Anthopoulos, M. J. Frampton, E. B. Namdas,
P. L. Burn, I. D. W. Samuel. Adv. Mater. 2004, 16, 557–560; c) C.
Adachi, M. A. Baldo, M. E. Thompson, S. R. Forrest, J. Appl. Phys.
2001, 90, 5048–5051; d) E. Tekin, E. Holder, V. Marin, B.-J.
de Gans, U. S. Schubert, Macromol. Rapid Commun. 2005, 26, 293–
297; e) E. Holder, V. Marin, D. Kozodaev, M. A. R. Meier, B. G. G.
Lohmeijer, U. S. Schubert, Macromol. Chem. Phys. 2005, 206, 989–
997.
[3]a) J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K.
Mackay, R. H. Friend, P. L. Burns, A. B. Holmes, Nature 1990, 347,
539–541; b) C. Adachi, M. A. Baldo, S. R. Forrest, S. Lamansky,
M. E. Thompson, R. C. Kwong, Appl. Phys. Lett. 2001, 78, 1622–
1624; c) G. E. Jabbour, J. F. Wang, N. Peyghambarian, Appl. Phys.
Lett. 2002, 80, 2026–2028; d) J. P. Duan, P. P. Sun, C. H. Cheng, Adv.
Mater. 2003, 15, 224–228; e) S. Lamansky, P. Djurovich, D. Murphy,
F. Abdel-Razzaq, H.-E. Lee, C. Adachi, P. E. Burrows, S. R. Forrest,
M. E. Thompson, J. Am. Chem. Soc. 2001, 123, 4304–4312.
[4]a) M. A. Baldo, S. Lamansky, P. E. Burrows, M. E. Thompson, S. R.
Forrest, Appl. Phys. Lett. 1999, 75, 4–6; b) M. J. Frampton, E. B.
Namdas, S.-C. Lo, P. L. Burn, I. D. W. Samuel, J. Mater. Chem. 2004,
14, 2881–2888.
[5]a) K. M. Vaeth, C. W. Tang, J. Appl. Phys. 2002, 92, 3447–3453;
b) A. Dijken, J. J. A. M. Bastiaansen, N. M. M. Kiggen, B. M. W.
Langeveld, C. Rothe, A. Monkman, I. Bach, P. Stçssel, K. Brunner,
J. Am. Chem. Soc. 2004, 126, 7718–7727; c) K. Brunner, A. Dijken,
H. Bçrner, J. J. A. M. Bastiaansen, N. M. M. Kiggen, B. M. W. Lan-
geveld, J. Am. Chem. Soc. 2004, 126, 6035–6042; d) C. Y. Jiang, W.
Yang, J. B. Peng, S. Xiao, Y. Cao, Adv. Mater. 2004, 16, 537–541.
[6]a) H. Y. Zhen, C. Y. Jiang, W. Yang, J. X. Jiang, F. Huang, Y. Cao,
Chem. Eur. J. 2005, 11, 5007–5016; b) Z. Wang, A. R. McWilliams,
C. E. B. Evans, X. Lu, S. Chung, M. A. Winnik, I. Manners, Adv.
Funct. Mater. 2002, 12, 415–419.
[7]X. Chen, J.-L. Liao, Y. Liang, M. O. Ahmed, H.-E. Tseng, S.-A.
Chen, J. Am. Chem. Soc. 2003, 125, 636–637.
[8]A. J. Sandee, C. K. Williams, N. R. Evans, J. E. Davies, C. E. Boot-
hby, A. Kçhler, R. H. Friend, A. B. Holmes, J. Am. Chem. Soc.
2004, 126, 7041–7048.
PFO-Ir4: 1H NMR (400 MHz, CDCl3): d=7.67–7.85 (m, 6H), 2.12 (m,
4H), 0.95–1.38 (m, 20H), 0.59–0.82 (m, 10H), 9.02 (m, 3.6%4H; ArH
of Ir complex), 8.30 (m, 3.6%4H; ArH of Ir complex), 7.10 (m, 3.6%
2H; ArH of Ir complex), 6.85 ppm (m, 3.6%2H; ArH of Ir complex);
13C NMR (100 MHz, CDCl3): d=152.05, 140.72, 140.25, 129.03, 127.45,
126.40, 121.72, 120.22, 55.60, 40.63, 32.04, 31.21, 30.28, 29.48, 24.15, 22.85,
14.33 ppm; elemental analysis calcd (%): C 86.83, H 9.88, N 0.47; found:
C 85.47, H 10.01, N 0.43. According to the NMR data, the Ir complex
content in the copolymer was around 3.6%.
PFO-Ir8: 1H NMR (400 MHz, CDCl3): d=7.67–7.85 (m, 6H), 2.12 (m,
4H), 0.95–1.36 (m, 20H), 0.60–0.85 (m, 10H), 9.02 (m, 5.5%4H; ArH
of Ir complex), 8.30 (m, 5.5%4H; ArH of Ir complex), 7.10 (m, 5.5%
2H; ArH of Ir complex), 6.86 ppm (m, 5.5%2H; ArH of Ir complex);
13C NMR (100 MHz, CDCl3): d=152.04, 140.72, 140.25, 129.03, 127.44,
126.39, 121.72, 120.21, 55.57, 40.63, 32.03, 31.19, 30.27, 29.46, 24.14, 22.84,
14.32 ppm; elemental analysis calcd (%): C 86.50, H 9.76, N 0.70; found:
C 84.54, H 9.87, N 0.60. According to the NMR data, the Ir complex con-
tent in the copolymer was around 5.5%.
[9]J. X. Jiang, C. Y. Jiang, W. Yang, H. Y. Zhen, F. Huang, Y. Cao,
Macromolecules 2005, 38, 4072–4080.
[10]a) C. L. Lee, N. G. Kang, Y. S. Cho, J. S. Lee, J. J. Kim, Opt. Mater.
2002, 21, 119–123; b) S. Tokito, M. Suzuki, F. Sato, M. Kamachi, K.
Shirane, Org. Electron. 2003, 4, 105–111; c) X. D. Wang, K. Ogino,
PFO-Ir16: 1H NMR (400 MHz, CDCl3): d=7.67–7.85 (m, 6H), 2.12 (m,
4H), 0.95–1.36 (m, 20H), 0.63–0.86 (m, 10H), 9.02 (m, 11%4H; ArH
4360
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Chem. Eur. J. 2006, 12, 4351 – 4361