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Pt(II) diynes and polyynes incorporating 5,5′- and 6,6′-disubstituted 2,2′-bipyridines were prepared following conventional Sonogashira and Hagihara dehydrohalogenation reaction protocols. Using Pt(II) dimers and polymers as a rigid-rod backbone, four new heterobimetallic compounds incorporating Re(CO)₃Cl as a pendant functionality in the 2,2′-bipyridine core were obtained. The new heterobimetallic Pt–Re compounds were characterized by analytical and spectroscopic techniques. The solid-state structures of a Re(I)-coordinated diterminal alkynyl ligand and a representative model compound were determined by single-crystal X-ray diffraction. Detailed photophysical characterization of the heterobimetallic Pt(II) diynes and polyynes was carried out. We find that the incorporation of the Re(CO)₃Cl pendant functionality in the 2,2′-bipyridine-containing main-chain Pt(II) diynes and polyynes has a …