Dinuclear Ru/Ni, Ir/Ni, and Ir/Pt Complexes with Bridging Phenanthroline-5,6-dithiolate: Synthesis, Structure, and Electrochemical and Photophysical Behavior

作者：Schallenberg David; Neubauer Antje^*; Erdmann Elisa; Taenzler Marco; Villinger Alexander; Lochbrunner Stefan; Seidel Wolfram W

来源：Inorganic Chemistry, 2014, 53(17): 8859-8873.

DOI：10.1021/ic4031206

We report the synthesis and full characterization of dinuclear complexes with the bridging ligand phenanthroline-5,6-dithiolate (phendt(2-)) featuring the [Ru(bpy)(2)](2+) or Ir(ppy)(2)](+) fragment at the diimine donor center and the [Ni(dppe)](2+) or [Pt(phen)](2+) complex moiety at the dithiolate group. The molecular structures of the mononuclear complexes [(C5H5)(2)Ti(S,S%26apos;-phendt)] and [(ppy)(2)Ir{N,N%26apos;-phendt-(C2H4CN)(2)}](PF6) as well as the dinuclear complex [(C5H5)(PPh3)Ru(phendt)Ni(dppe)](PF6) determined by X-ray diffraction (XRD) studies are compared. Photophysical studies with mononuclear [(bpy)(2)Ru{phendt-(C2H4CN)(2)}](2+) and [(ppy)(2)Ir{phendt(C2H4CN)(2)}](+) as well as dinudear [(bpy)(2)Ru(phendt)Ni(dppe)](2+) and [(ppy)(2)Ir(phendt)Ni(dppe)r uncovered an effective luminescence quenching in the dinuclear complexes. Lifetime measurements at room temperature, steady-state measurements at low temperature, electrochemical investigations, and DFT calculations provide evidence for a very efficient energy transfer from the Ru/Ir to the Ni complex moiety with a rate constant k %26gt; 5 x 10(9) s(-1). In comparison, the [Ru]phendt[Ni] complex displays a higher quenching efficiency with reduced excited state lifetime, whereas the [Ir]phendt[Ni] complex is characterized by an unaltered lifetime of the thermally equilibrated excited state.

• 出版日期2014-9-1