Evolution of lowest singlet and triplet excited states with transition metals in group 10–12 metallaynes containing biphenyl spacer

A new series of thermally stable group 10 platinum(II) and group 12 mercury(II) poly-yne polymers containing biphenyl spacer trans-[–Pt(PBu3)2CC(p-C6H4)2CC–]n and [HgCC(p-C6H4)2CC–]n were prepared in good yields by Hagihara’s dehydrohalogenation reaction of the corresponding metal chloride precursors with 4,4′-diethynylbiphenyl HCC(p-C6H4)2CCH at room temperature. We report the optical spectroscopy of these polymetallaynes and compare the results with their bimetallic model complexes trans-[Pt(Ph)(PEt3)2CC(p-C6H4)2CCPt(Ph)(PEt3)2] and [MeHgCC(p-C6H4)2CCHgMe] as well as the group 11 gold(I) counterpart [(PPh3)AuCC(p-C6H4)2CCAu(PPh3)]. The structural properties of all model complexes have been studied by X-ray crystallography. The influence of the heavy metal atom in these metal alkynyl systems on the intersystem crossing rate and the spatial extent of lowest singlet and triplet excitons is systematically characterized. Our investigations indicate that the organic triplet emissions can be harvested by the heavy-atom effect of group 10–12 transition metals (viz., Pt, Au, and Hg) which enables efficient intersystem crossing from the S1 singlet excited state to the T1 triplet excited state.

A series of metal di-ynes and poly-ynes of group 10–12 transition elements containing biphenyl spacer moiety are prepared and characterized. A discussion on the heavy-atom effect of Pt(II), Au(I) and Hg(II) ions in harvesting the organic triplet emissions in such phosphorescent metal-organic systems is made and the influence of the metal center on the spatial extent of lowest singlet and triplet excited states is characterized in detail.Figure optionsDownload as PowerPoint slide