Novel acetylene monomers containing N-phenyl-substituted carbazole (Cz) and triphenylamine (TPA) groups, namely, 3-ethynyl-9-phenylcarbazole (1) and p-(N,N-diphenylamino)phenylacetylene (2) were synthesized, and polymerized with several Rh-, W-, and Mo-based catalysts. Poly(l) and poly(2) with high number-average molecular weights (15500-974000) were obtained in good yields (77-97%), when [(nbd)RhCl](2)-Et3N (nbd = norbomadiene) was used as a catalyst. The polymers exhibited UV-vis absorption peaks derived from the Cz and TPA moieties at 250-350 nm and polyacetylene backbone above 350 nm. The UV-vis absorption band edge wavelengths of the polymers were longer than those of the corresponding monomers. Poly(2) exhibited a UV-vis absorption peak at a longer wavelength than poly(1) did, which indicates that poly(2) has main chain conjugation longer than that of poly(l). The molecular weights and photoluminescence quantum yields of the polymers obtained by the polymerization using [(nbd)RhCl](2)-Et3N were larger than those of the Rh+(nbd)[eta(6)-C6H5B-(C6H5)(3)]-based counterparts. The cyclic voltammograms of the polymers indicated that they had clear electrochemical properties; the onset oxidation voltage of poly(1) was higher than those of N-alkyl-substituted Cz derivatives. The polymers showed electrochromism and changed the color from pale yellow to blue by application of voltage, presumably caused by the formation of charged polaron at the Cz and TPA moieties. The temperatures for 5% weight loss of the polymers were around 350-420 degrees C under air, indicating the high thermal stability. (c) 2006 Elsevier Ltd. All rights reserved.