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(Co)Polymers containing pentafluorophenylacetylene (F5PA) have been prepared for the first time mediated by [Rh(nbd)Cl]2/NEt3 to give materials with properties typical of poly(phenylacetylene)s prepared with this catalyst/co‐catalyst combination. It is demonstrated that the F5PA repeat units in these new (co)polymers serve as convenient reactive species for post‐polymerization modification with thiols...
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