Different structural preference of Ag(i) and Au(i) in neutral and cationic luminescent heteropolynuclear platinum(ii) complexes: Z (U)-shaped Pt2M2 type vs. trinuclear PtM2 type

Abstract

The reactions of monocationic Pt(II) complexes bearing N^C chelate ligands and Me₂pzH, [Pt(N^C)(Me₂pzH)₂]PF₆ (N^C = 2-phenylpyridinate (ppy⁻), 2-(2,4-difluorophenyl)pyridinate (dfppy⁻), benzo[h]quinolinate (bzq⁻); Me₂pzH = 3,5-dimethylpyrazole), with Ag(I) ions gave Z (or U)-shaped neutral tetranuclear Pt₂Ag₂ complexes [Pt₂Ag₂(N^C)₂(Me₂pz)₄], while those with Au(I) ions gave neutral trinuclear PtAu₂ complexes [PtAu₂(N^C)(Me₂pz)₃]. On the contrary, the reactions of the dicationic Pt(II) complex bearing a N^N chelate ligand and Me₂pzH, [Pt(bpy)(Me₂pzH)₂](PF₆)₂ (bpy = 2,2′-bipyridine), with Ag(I) and Au(I) ions both gave Z (or U)-shaped dicationic tetranuclear Pt₂M₂ complexes, [Pt₂M₂(bpy)₂(Me₂pz)₄](PF₆)₂ (M = Ag, Au). The structures of heteropolynuclear Pt(II) complexes were dominated by the nature of incorporated group 11 metal ions and the charge of complexes.