POLYMERIZATION OF N-CARBAZOLYLACETYLENE BY VARIOUS TRANSITION-METAL CATALYSTS AND POLYMER PROPERTIES

N-Carbazolylacetylene (CzA) was polymerized in the presence of various transition metal catalysts including WCl6, MoCl5, [Rh(NBD)Cl](2), and Fe(acac)(3) to give polymers in good yields. The polymers produced wi th W catalysts were dark purple solids and soluble in organic solvents such as toluene, chloroform, etc. The highest weight-average molecula r weight of poly(CzA) reached about 4 x 10(4). In the UV-visible spect rum in CHCl3, poly(CzA) exhibited an absorption maximum around 550 nm (epsilon(max) = 4.0 x 10(3) M-1 cm(-1)) and the cutoff wavelength was 740 nm, showing a large red shift compared with that of poly(phenylace tylene) [poly(PA)]. Poly(CzA) began to lose weight in TGA under air at 310 degrees C, being thermally more stable than poly(PA) and poly[3-( N-carbazolyl)-1-propyne]. Poly(CzA) showed a third-order susceptibilit y of 18 x 10(-12) esu, which was 2 orders larger than that of poly(PA) . (C) 1998 John Wiley & Sons, Inc.