3-Ethynyl-4-(trimethylsilyl)thiophene (1a) and 3-ethynyl-4-bromothiophene (1b) selectively undergo acetylene polymerizations in the presence of the MoCl5- and WCl6-Ph3SiH catalysts to give soluble, high-molecular-weight poly(thienylacetylenes) (2) (M-w up to 602000) in high yields (up to 100\\%). Light transmission spectra of THF solutions of 2 continuously red-shift with increasing concentration. The concentratochromism shows a logarithmic concentration dependence; that is, the optical transitions of 2 are predictably tunable by simply changing their concentrations.
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