Utilization of Sonogashira coupling reactions with cis-[Pt(dppe)Cl2] and varying amounts of the alkynyl ligands HC⋮CRC⋮CH (where R = p -C6H4, p -C6H4-p -C6H4) afford the monoplatinum complexes cis-[Pt(dppe)(C⋮CRC⋮CH)2] (R = p -C6H4 (1a), p -C6H4-p -C6H4 (1b)), the diplatinum complexes cis-[(HC⋮CRC⋮C)Pt(dppe)(C⋮CRC⋮C)Pt(dppe)(C⋮CRC⋮CH)] (R = p -C6H4 (2a), p -C6H4-p -C6H4 (2b)), the triplatinum complexes cis-[(HC⋮CRC⋮C)Pt(dppe)(C⋮CRC⋮C)Pt(dppe)(C⋮CRC⋮C)Pt(dppe)(C⋮CRC⋮CH)] (R = p -C6H4 (3a), p -C6H4-p -C6H4 (3b)), and the respective oligomeric species 4a,b, all in reasonable yields. X-ray diffraction studies of 2a reveal the presence of two independent diplatinum molecules in the asymmetric unit, each with C i symmetry. All the complexes have been fully characterized by NMR and mass spectrometry, and GPC analysis of 4a,b indicate their oligomeric nature, with a degree of polymerization of ca. 4. Electronic spectral studies indicate that the optical band gap decreases with increasing chain length but that the intensity of the triplet state emission increases with the number of repeating units. As expected, there is less effective π-conjugation along the chain in the cis configuration as compared to the analogous trans-oriented species.

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Summary: The synthesis and thermal, redox and photoluminescence properties of a soluble donor‐acceptor polyplatinayne with the electron‐accepting silole ring and its model compound are described. The polymer has an optical band gap of 2.10 eV which is much lower than that of thienyl‐ or silyl‐bridged congeners. The incorporation of electron‐accepting silole unit in the metallopolymer main chain creates a new π‐conjugated system that features unique donor‐acceptor characteristics.