Abstract: | The novel trans‐stereo‐regular silylene–thiophene derivatives ( 4 , 5 ) with perfect consecutive silylene–arylene–silylene–vinylene linkage were synthesized via silylative coupling polycondensation of 2,5‐bis(vinyldimethylsilyl)thiophene ( 2 ) or 5,5′‐bis(vinyldimethylsilyl)‐2,2′‐bithiophene ( 3 ) catalyzed by ruthenium‐hydride complex [RuHCl(CO)(PCy3)2] ( 1 ). Their spectroscopic, absorption, and luminescence properties were characterized and compared with those of model compounds containing thiophene or bithiophene chromophores. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 127–137, 2008 |