Macromolecules, Vol. 38, No. 11, 2005
Blue Highly Fluorescent Vinyl Polymers 4703
(2) (a) Tang, C. W.; VanSlyke, S. A.; Chen, C. H. J. Appl. Phys.
1989, 3610. (b) Burroughes, J. H.; Bradley, D. D. C.; Brown,
A. R.; Marks, R. N.; Mackay, K.; Friend, R. H.; Burns, P. L.;
Holmes, A. B. Nature (London) 1990, 347, 539. (c) Braun,
D.; Heeger, A. J. Appl. Phys. Lett. 1991, 58, 1982. (d) Kepler,
R. G.; Beeson, P. M.; Jacobs, S. J.; Anderson, R. A.; Sinclair,
M. B.; Valencia, V. S.; Cahill, P. A. Appl. Phys. Lett. 1995,
66, 3618. (e) Thompson, M. A.; Forrest, S. R. Nature (London)
2000, 403, 750. (f) Srdanov, G.; Wudl, F. U.S. Patent No. 5,-
189,136, 1993. (g) Lee, S. H.; Nakamura, T.; Tsutsui, T. Org.
Lett. 2001, 3, 2006. (h) Noda, T.; Shirota, Y. J. Am. Chem.
Soc. 1998, 120, 971. (i) Sheats, J. R.; Antoniadis, H.; Hue-
schen, M.; Leonard, W.; Miller, J.; Moon, R.; Roitman, D.;
Stocking, A. Science 1996, 273, 884. (j) Goldfinger, M. B.;
Crawford, K. B.; Swager, T. M. J. Am. Chem. Soc. 1997, 119,
4578. (k) Neef, C. J.; Ferraris, J. P. Macromolecules 2000,
33, 2311. (l) Pei, Q.; Yang, Y. J. Am. Chem. Soc. 1996, 118,
7416. (m) Ego, C.; Marsitzky, D.; Becker, S.; Zhang, J.;
Grimsdale, A. C.; Mu¨llen, K.; MacKenzie, J. D.; Silva, C.;
Friend, R. H. J. Am. Chem. Soc. 2003, 125, 437. (n) Holms,
R. J.; Andrade, B. W.; Forrest, S. R. Appl. Phys. Lett. 2003,
83, 3819.
(3) (a) Chen, C. H.; Shi, J. Coord. Chem. Rev. 1998, 171, 161. (b)
Kido, J.; Okamoto, Y. Chem. Rev. 2002, 102, 2357.
(4) Burroughes, J. H.; Bradley, D. D. C.; Brown, A. R.; Marks,
R. N.; Mackay, K.; Friend, R. H.; Burn, P. L.; Holms, A. B.
Nature (London) 1990, 347, 539.
(5) (a) Cheng, Y.; Ma, B.; Wudl, F. J. Mater. Chem. 1999, 9, 2183.
(b) Mitsumori, T.; Bendikov, M.; Sedo´, J.; Wudl, F. Chem.
Mater. 2003, 15, 3759.
(6) (a) Carreira, E. M.; Du-Bois, J. J. Am. Chem. Soc. 1995, 117,
8106. (b) Roark, W. H.; Tinney, F. J.; Cohen, D.; Essenburg,
A. D.; Kaplan, H. R. J. Med. Chem. 1985, 28, 1291.
(20 mL). The precipitate was centrifuged, and the solid was
collected. The solid was dissolved in CH2Cl2 (10 mL), and the
solution was added to MeOH (50 mL) with stirring. The pre-
cipitate was separated by centrifuging and dried under reduced
pressure for 24 h. Purification was accomplished by dissolving
the solid in CH2Cl2 (10 mL) and being precipitated with
2-propanol (50 mL) to afford a white powder that was isolated
by filtration and dried under vacuum for 4 days at 60 °C.
Poly(pyrrolo[1,2-b]pyridazine-5,6,7-tricarboxylic acid
5,6-dimethyl ester 7-(4-vinylbenzyl) ester) (PPS). In 44%
1
yield. H NMR (CDCl3): δ 8.5-8.3 (br, 2H), 7.3-6.9 (br, 3H),
6.7-6.2 (br, 2H), 5.4-5.0 (br, 2H), 3.9-3.7 (br, 3H), 3.7-3.4
(br, 3H), 2.2-0.9 (br, 3H). 13C NMR (CDCl3): δ 165.2, 162.5,
158.8, 145.0, 133.0, 131.7, 129.1, 127.5-128.4 (br), 117.7, 116.8,
102.6, 66.7, 52.4-52.8 (br), 51.8, 40.0-40.5 (br). Elemental
analysis for C21H18N2O6: Calcd C, 63.91; H, 4.80; N, 7.10.
Found C, 63.32; H, 4.37; N, 6.85. IR: ν (CdO) 1735, 1722, 1710
cm-1
.
Poly(pyrrolo[1,2-b]pyridazine-5,6,7-tricarboxylic acid
5,6-dimethyl ester 7-[2-(2-methylacryloyloxy)ethyl] es-
1
ter) (PPM1). In 44% yield. H NMR (CDCl3): δ 8.5-8.2 (br,
2H), 7.1-6.9 (br, 1H), 4.6-4.0 (br, 4H), 4.0-3.9 (br, 3H), 3.9-
3.8 (br, 3H), 2.3-1.2 (br, 2H), 1.1-0.6 (br, 3H). Elemental
analysis for C17H18N2O7: Calcd C, 56.35; H, 5.01; N, 7.73.
Found C, 56.72; H, 4.71; N, 7.28. IR: ν (CdO) 1739, 1722, 1709
cm-1
.
Poly(pyrrolo[1,2-b]pyridazine-5,6,7-tricarboxylic acid
5,6-dimethyl ester 7-[2-(2-methylacryloyloxy)ethyl] ester-
co-methyl methacrylate) (1:2) (PPM2). Pyrrolo[1,2-b]py-
ridazine-5,6,7-tricarboxylic acid 5,6-dimethyl ester 7-[2-(2-
methylacryloyloxy)ethyl] ester (5) (181 mg, 0.5 mmol) and
methyl methacrylate (100 mg, 1.0 mmol) were used together
as monomers, and PPM2 was obtained in 38% yield according
to the general method of polymerization. 1H NMR (CDCl3): δ
8.6-8.4 (br, 2H), 7.2-7.0 (br, 1H), 4.6-4.4 (br, 2H), 4.4-4.1
(br, 2H), 4.05-3.95 (br, 3H), 3.95-3.85 (br, 3H), 3.7-3.3 (br,
6H), 2.2-1.1 (br, 6H), 1.1-0.6 (br, 9H). Elemental analysis
for C27H34N2O11: Calcd C, 57.64; H, 6.09; N, 4.98. Found C,
(7) (a) Fieser, M. Fieser and Fieser’s Reagents for Organic
Synthesis; Wiley: New York, Vol. 10, p 41. (b) Diago-
Meseguer, J.; Palomo-Coll, A. L.; Fernandez-Lizarbe, J. R.;
Zugaza-Bibao, A. Synthesis 1980, 547.
(8) Odian, G. Principles of Polymerization; John Wiley & Sons:
New York, 1976.
(9) Patnode, W.; Scheiber, W. J. J. Am. Chem. Soc. 1939, 61,
3449.
56.85; H, 5.84; N, 4.91. IR: ν (CdO) 1724, 1711 cm-1
.
(10) Brandup, J.; Immergut, E. H.; Grulke, E. A. Abe, A.; Bloch,
Fabrication of Waveguides. (1) Fiber of PPS. A 5 mL
vessel was charged with polymer PPS (100 mg) in CH2Cl2 (0.5
mL). The mixture was stirred with a glass rod (diameter 0.3
cm) for 10 min. From the viscous mixture a fiber was pulled
up slowly (30 mm/1 min) with the glass rod. The size of the
obtained fiber was 0.5 × 0.5 × 30 mm.
D. R. Polymer Handbook, 4th ed.; Wiley: New York, 1999.
(11) Losherk, S. J. Polym. Sci. 1955, 15, 391.
(12) (a) Willardson, R. K.; Weber, E.; Mueller, G.; Sato, Y.
Electroluminescence I, Semiconductors and Semimetals Se-
ries; Academic Press: New York, 1999. (b) Bulovic, V.;
Forrest, S. R.; Mueller-Mach, R.; Mueller, G. O.; Leslela, M.;
Li, W.; Ritala, M.; Neyts, K.; Electroluminescence II Semi-
conductors and Semimetals Series; Academic Press: New
York, 2000.
(2) Rod of 9,10-Diphenylanthracene and Polystyrene.
A 5 mL vessel was charged with polystyrene (190 mg) and
9,10-diphenylanthracene (10 mg). The mixture was stirred
with a glass rod (diameter 0.3 cm) and heated around 150 °C
for 10 min. From the viscous melt a rod was pulled up slowly
(100 mm/1 min) with the glass rod. The size of the obtained
rod was 2 × 2 × 200 mm.
(13) Sharma, A.; Schulman, S. G. Fluorescence Spectroscopy; John
Wiley & Sons: New York, 1999.
(14) (a) Zheng, M.; Bai, F.; Zhu, D. Polym. Adv. Technol. 1999,
10, 476. (b) Ng, S. C.; Ding, D.; Chan, H. S. O.; Yu, W. L.
Macromol. Chem. Phys. 2001, 202, 8. (c) Pu, Y. J.; Soma, M.;
Tsuchida, E.; Nishide, H. J. Polym. Sci., Part A: Polym.
Chem. 2000, 38, 4119. (d) Bunten, K. A.; Kakkar, A. K.
Macromolecules 1996, 29, 2885. (e) Xu, B.; Zhang, J.; Peng,
Z. Synth. Met. 2000, 113, 35. (f) Ng, S. C.; Xu, L. G.; Chan,
H. S. O.; Yu, W. L. Synth. Met. 1998, 94, 185.
(15) Nguyen, T. Q.; Doan, V. Schwartz, B. J. J. Chem. Phys. 1999,
110, 4068.
(16) (a) McRae, E. J. Phys. Chem. 1957, 61, 562. (b) Becker, R. S.
Theory and Interpretations of Fluorescence and Phosphores-
cence; John Wiley & Sons: New York, 1969.
Acknowledgment. We are grateful to Dr. M. Bendik-
ov (Department of Chemistry and Biochemistry, UCLA)
for DSC and TGA measurements and Prof. Y. Yang
(Department of Engineering, UCLA) for instructive
discussion. We are grateful to Mitsubishi Chemical
Corp. for support of T.M. We also thank the ONR for
support through a grant (N00014-97-1-0835).
(17) Van der Veen, R. H.; Cerfontain, H. Tetrahedron 1985, 41,
References and Notes
585.
(1) (a) Tullo, A. H. Chem. Eng. News 2000, 78, 25. (b) Tang, C.
W.; Van Slyke, S. A. Appl. Phys. Lett. 1987, 51, 913. (c) Woo,
H. S.; Czerw, R.; Webster, S.; Carroll, D. L.; Ballato, J.;
Strevens, A. E.; O’Brien, D.; Blau, W. J. Appl. Phys. Lett.
2000, 77, 1393. (d) Chen, L.; McBranch, D. W.; Wang, H.-L.;
Helgeson, R.; Wudl, F.; Whitten, D. C. Proc. Natl. Acad. Sci.
U.S.A. 1999, 96, 12287. (e) Hide, F.; D´ıaz-Garc´ıa, M. A.;
Schwartz, B. J.; Andersson, M.; Pei, Q.; Heeger, A. J. Science
1996, 273, 1833. (f) Swager, T. M. Acc. Chem. Res. 1998, 31,
201. (g) Pei, Q.; Yu, G.; Zhang, C.; Yang, Y.; Heeger, A. J.
Science 1995, 269, 1086. (g) Xia, H.; Zhang, C.; Qui, S.; Lu,
P.; Zhang, J.; Ma, Y. Appl. Phys. Lett. 2004, 84, 291.
(18) (a) Tomozawa, H.; Braun, D.; Phillips, S.; Heeger, A, J.;
Kroemer, H. Synth. Met. 1987, 22, 63. (b) Heeger, A. J.;
Kivelson, S.; Schrieffer, J. R.; Su, W. R. Rev. Mod. Phys. 1988,
60, 781.
(19) Fumitomo, H,; Diaz-Garcia, M. A.; Schwartz, B. J.; Anders-
son, M. R.; Pei, Q.; Heeger, A. J. Science 1996, 273, 1833.
(20) (a) Kruhlak, R. J.; Kuzyk, M. G. J. Opt. Soc. Am. B 1999, 16,
1749. (b) Kruhlak, R. J.; Kuzyk, M. G. J. Opt. Soc. Am. B
1999, 16, 1756.
(21) Krug, W.; Miao, E.; Derstine, M.; Valera, J. J. Opt. Soc. Am.
B 1989, 6, 726.