Tailor-made poly(vinylidene sulfide)s by Rh(I)–NHC catalyzed regioselective thiol-yne click polymerization

•The [Rh(μ-Cl)(IPr)(η2-coe)]2/pyridine system catalyzes the polyhydrothiolation of dialkynes with dithiols.•Poly(vinylidene sulfide)s have been prepared by regioselective thiol-yne click polymerization.•Copolymerization of flexible dithiols with rigid aromatic dialkynes yields very high molecular weight poly(vinylidene sulfide)s.•Markovnivov regioselectivity is determined by the synergistic effect of the IPr and pyridine ligands on the catalyst.