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Table 1. Results of the Preparation of PPympyms and UV-Vis Data of the Polymers
absorption, max, nme (, M-1 cm-1)
no. polymera yield, % Mnd
1 PPympym-1 60 445 (770) 473 (6900)f
2 PPympym-2 90 (60c) 8000 425 (7300) 451 (7600) 483 (3000)
3b PPympym-2 90 8800 427 (6900) 452 (9000) 483 (4000)
4 PPympym-3 93 10 000 423 (7000) 448 (7100) 480 (3500)
5 PPympym-4 99 5000 427 (7700) 449 (8200) 479 (3700)
6 PPympym-5 98 7000 424 (7700) 448 (8300) 478 (3300)
7 PPympym-6 90 (64c) 9000 431 (12800) 457 (12300)
a Prepared by dehalogenation polycondensation using the nickel complex. Solvent used for polymerization ) DMF, unless otherwise
noted. b Prepared in toluene. c Yield after purification by reprecipitation. d Determined by GPC (polystyrene standards). PPympym-1;
not measured due to poor solubility in chloroform. e Solvent ) CHCl3, unless otherwise noted. Molarity for the calculation of is based
on the repeating unit. The value for the peak at the longest wavelength (478-483 nm for PPympym-2 through -5) depends on the
measuring conditions. f Solvent ) formic acid.
1H
Figure 1. NMR spectrum of PPympym-2 in CDCl3.
Figure 6. Plots of the d value vs the number of carbons in Figure 8. Cyclic voltammogram of a film of PPympym-2 on
the R group in the polymer. a Pt plate in an acetonitrile solution of [(C2H5)4N]BF4 (0.10
M). Sweep rate is 70 mV s-1 at room temperature.
(CH2)5), 0.88 (t, 6H, CH3). 13C{1H} NMR (CDCl3, ppm): (2) (a) Yamamoto, T.; Sugiyama, K.; Kushida, T.; Inoue, T.;
158.93 (4,8-C), 154.60 (2,6-C), 131.33 (4a, 8a-C), 40.85 (C1 of Kanbara, T. J. Am. Chem. Soc. 1996, 118, 3930. (b) Yama-
octyl group), 31.79 (C2), 29.27 (C3), 29.23 (C4), 29.18 (C5), 26.96 moto, T. Bull. Chem. Soc. Jpn. 1999, 72, 621. (c) Yamamoto,
(C6), 22.63 (C7), 14.07 (C8). T.; Yamamoto, A. Chem. Lett. 1977, 353.
(3) (a) McCullough, R. D.; Lowe, R. D. J. Chem. Soc., Chem.
Polymerization. The polymers were prepared by using an
Commun. 1992, 70. (b) McCullough, R. D.; Tristam-Nagle,
Ni(0) complex. Details of the preparation as well as analytical S.; Willams, S. P.; Lowe, R. D.; Jayaraman, M. J. Am. Chem.
and spectroscopic data of the polymers are described below. Soc. 1993, 115, 4910. (c) McCullough, R. D. Adv. Mater. 1998,
PPympym-2. To a DMF solution (20 mL) containing Ni- 10, 93.
(cod)2 (0.40 g, 1.5 mmol), cod (0.3 mL), and bpy (0.26 g, 1.6 (4) (a) Chen, T.-A.; Rieke, R. D. J. Am. Chem. Soc. 1992, 114,
mmol) was added 2,6-dichloro-4,8-bis(N-octylamino)pyrimido- 10087. (b) Chen, T.-A.; Wu, X.; Rieke, R. D. J. Am. Chem.
[5,4-d] pyrimidine (0.46 g, 1.0 mmol) with stirring. The reaction Soc. 1995, 117, 233.
mixture was stirred at 60 C for 48 h to afford a red precipitate. (5) Setayesh, S.; Grimsdale, A. C.; Weil, T.; Enkelmann, V.;
The precipitate was collected by filtration, washed with Mullen, K.; Meghdadi, F.; List, E. J. W.; Leising, G. J. Am.
Chem. Soc. 2001, 123, 946.
aqueous ammonia, a warm aqueous solution of EDTA (ethyl- (6) (a) Politis, J. K.; Nemes, J. C.; Curtis, M. D. J. Am. Chem.
enediaminetetraacetic acid), warm distilled water, and metha- Soc. 2001, 123, 2537. (b) Nanos, J. I.; Kampf, J. W.; Curtis,
nol in this order. Drying under vacuum at 60 C for 40 h gave M. D.; Gonzalez, L.; Martin, D. C. Chem. Mater. 1995, 7, 2332.
an orange-red powder of the polymer, PPympym-2, in 90% (7) (a) Bunz, U. H. F. Chem. Rev. 2000, 100, 1605. (b) Sanechika,
yield. The obtained polymer was further dissolved in CHCl3 K.; Yamamoto, T.; Yamamoto, A. Bull. Chem. Soc. Jpn. 1984,
and reprecipitated in acetone to give samples for the instru- 57, 752. (c) Yamamoto, T.; Yamada, W.; Takagi, M.; Kizu,
mental analysis (yield ) 60%). Anal. Calcd for (C22H36N6 K.; Maruyama, T.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino,
0.2H2O)n: C, 68.1; H, 9.5; N, 21.7. Found: C, 68.0; H, 9.6; N, T.; Kubota, K. Macromolecules 1994, 32, 6620.
(8) Peng, Z. G.; Gharavi, A. R.; Yu, L. J. Am. Chem. Soc. 1997,
20.3. IR (KBr, cm-1): 3290, 2924, 2854, 1591, 1465, 1387, 1141,
119, 4622.
865, 720, 673. 1H NMR (CDCl3, ppm): 9.08 (2H, NH), 1.2- (9) Hu, Q.-S.; Vitharana, D.; Liu, G.; Jain, V.; Pu, L. Macromol-
4.4 (28H, CH2), 0.90 (6H, CH3). 13C{1H} NMR (CDCl3, ppm): ecules 1996, 29, 5075.
159.39 (4,8-C), 157.07 (2,6-C), 131.96 (4a, 8a-C), 41.74 and (10) (a) Yamamoto, T.; Komarudin, D.; Arai, M.; Lee, B.-L.;
41.08 (C1 of the octyl group), 32.03 and 31.87 (C2), 31.83 to Suganuma, H.; Asakawa, N.; Inoue, Y.; Kubota, K.; Sasaki,
28.83 (C3, C,4 and C5), 27.68 and 27.29 (C6), 22.78 and 22.67 S.; Fukuda, T.; Matsuda, H. J. Am. Chem. Soc. 1998, 120,
(C7), 14.11 (C8). Mn/Mw (GPC: polystyrene standards in CHCl3) 2047. (b) Yamamoto, T.; Lee, B.-L.; Suganuma, H.; Sasaki,
) 8000/15000. [] ) 0.15 dL g-1 (in CHCl3 at 30 C). S. Polym. J. 1998, 30, 853. (c) Halkyard, C. E.; Rampey, M.
Other polymers were prepared analogously. E.; Kloppenburg, L.; Studer-Martinez, S. L.; Bunz, U. H. F.
Macromolecules 1998, 31, 8655.
PPympym-1. Dark red powder (yield ) 60%). Anal. Calcd (11) (a) Jerome, D.; Bechgaard, K. Nature (London) 2001, 410,
for (C14H20N60.58H2O)n: C, 59.4; H, 7.5; N, 29.7. Found: C, 162. (b) Schone, J. H.; Dodabalapur, A.; Bao, Z.; Kloc, Z. B.;
59.1; H, 7.3; N, 28.4. IR (KBr, cm-1): 3302, 2958, 2930, 2870, Schenkar, O.; Batlogg, B. Nature (London) 2001, 410, 189.
1584, 1524, 1413, 1379, 1142, 857, 724, 671. (c) Sirringhaus, H.; Brown, P. J.; Friend, R. H.; Nielsen, M.
PPympym-3. Yellow powder (yield ) 93%). Anal. Calcd for M.; Bechgaard, K.; Langeveld-Boss, B. M. W.; Spiering, J.
(C26H44N61.0H2O)n: C, 68.1; H, 10.1; N, 18.3. Found: C, 68.6; H.; Janssen, R. A. J.; Maijer, E. W.; Herwig, P.; Leeuw, D.
H, 9.8; N, 18.1. IR (KBr, cm-1): 3290, 2924, 2852, 1588, 1528, M. Nature (London) 1999, 401, 685. (d) Yamamoto, T.;
1382, 1230, 1140, 857, 719, 672. Mn ) 10 000 (Mw/Mn ) 3.16). Kokubo, H.; Morikita, T. J. Polym. Sci., Part B: Polym. Phys.
PPympym-4. Dark red powder (yield ) 99%). Anal. Calcd 2001, 39, 1713.
(12) (a) Yamamoto, T.; Maruyama, T.; Zhou, Z.-H.; Ito, T.; Fukuda,
for (C30H52N62.5H2O)n: C, 66.5; H, 10.6; N, 15.5. Found: C, T.; Yoneda, Y.; Begum, F.; Ikeda, T.; Sasaki, S.; Takezoe, H.;
66.3; H, 9.9; N, 15.4. IR (KBr, cm-1): 3278, 2922, 2852, 1590, Fukuda, A.; Kubota, K. J. Am. Chem. Soc. 1994, 116, 4832.
1530, 145, 1388, 1141, 857, 719, 673. 1H NMR (CDCl3, ppm): (b) Saito, N.; Kanbara, T.; Nakamura, Y.; Yamamoto, T.;
9.08 (2H, NH), 1.3-4.2 (44H, CH2), 0.987 (6H, CH3). Mn ) Kubota, K. Macromolecules 1994, 27, 756. (c) Saito, N.;
5000 (Mw/Mn ) 1.23). Yamamoto, T. Macromolecules 1995, 28, 4260. (d) Yamamoto,
PPympym-5. Dark red powder (yield ) 98%). Anal. Calcd T.; Wakabayashi, S.; Osakada, K. J. Organomet. Chem. 1982,
for (C38H68N6)n: C, 74.9; H, 11.2; N, 13.8. Found: C, 73.1; H, 428, 223. (e) Yamamoto, T.; Nakamura, T.; Fukumoto, H.;
10.9; N, 13.3; Cl, 0.3. IR (KBr, cm-1): 3290, 2918, 2850, 1594, Kubota, K. Chem. Lett. 2001, 502.
(13) (a) Fischer, F. G.; Roch, J.; Neumann, W. P. Justus Liebigs
1538, 1467, 1388, 1140, 857, 718. Mn ) 7000 (Mw/Mn ) 1.24). Ann. Chem. 1960, 631, 147. (b) Fischer, F. G.; et al. US Patent
PPympym-6. Orange-red powder (yield ) 90%). Anal. 3,031,450. Patented Apr 24, 1962. (c) Yamamoto, T.; Lee, B.-
Calcd for (C20H32N6)n: C, 67.4; H, 9.0; N, 23.6. Found: C, 67.1; L. Tetrahedron Lett. 1999, 40, 535.
H, 9.0; N, 23.2. IR (KBr, cm-1): 2954, 2926, 2854, 1529, 1493, (14) Wait, S. C.; Wesley, J. W. J. Mol. Spectrosc. 1966, 19, 25.
1412, 1369, 1138, 1090, 857, 740. 1H NMR (CDCl3, ppm): (15) (a) Muramatsu, Y.; Yamamoto, T. Polymer 1999, 40, 6607.
3.28-4.82 (10H, N-CH3 and N-CH2), 1.72 and 1.25 (16H, (b) Muramatsu, Y.; Yamamoto, T.; Hasegawa, M.; Yagi, T.;
CH2), 0.79 (6H, CH3). 13C{1H} NMR (CDCl3, ppm): 160.33 Koinuma, H. Polymer 2001, 42, 6673.
(4,8-C), 155,98 (2,6-C), 136.39 (4a, 8a-C), 52.80 (N-CH3), 39.54 (16) Vahlenkamp, T.; Wegner, G. Macromol. Chem. Phys. 1994,
(C1 of the hexyl group), 32.32 (C2), 31.82 (C3), 28.38 (C4), 26.74 195, 1993.
(17) (a) Watanabe, J.; Harkness, B. R.; Sone, M.; Ichimura, H.
(C5), 22.66 (C6). Mn ) 9000 (Mw/Mn ) 1.79). Macromolecules 1994, 27, 507. (b) Jordan, E. F., Jr.; Felde-
isen, D. W.; Wrigley, A. N. J. Polym. Sci., Part A-1 1971, 9,
References and Notes 1835.
(18) (a) Yamamoto, T.; Etori, H. Macromolecules 1995, 28, 3371.
(1) (a) Skotheim, T. A.; Elsenbaumer, R. L.; Reynolds, J. P. (b) Lee, B.-L.; Yamamoto, T. Macromolecules 1999, 32, 1375.
Handbook of Conducting Polymers, 2nd ed.; Marcel Dekker: (19) Bogdanovic, B.; Kroner, M. Justus Liebigs Ann. Chem. 1966,
New York, 1997. (b) Nalwa, H. S. Handbook of Organic 699, 1.
Conductive Molecules and Polymers; John Wiley: New York,
1997. MA011632O