Synthesis of Re(I) Rings Comprising Different Re(I) Units and Their Light-Harvesting Abilities

Trimethylamine N-oxide (Me₃NO) could selectively remove only one CO ligand from fac-[Re(N^N)(CO)₃(PR₂R')]⁺ (N^N = diimine ligand), whereby only the CO ligand in the trans position to the phosphorus ligand was selectively removed to give cis,trans-[Re^I(N^N)(CO)₂(PR₂R')(L)] ⁿ⁺ in good yields. This decarbonylation reaction using Me₃NO was found to be especially useful for synthesizing biscarbonyl Re(I) complexes with electron-withdrawing groups in the diimine ligand, which could not be synthesized or were obtained only in low yields by the photochemical method. Me₃NO also selectively removed the carbonyl ligands in the trans position to the phosphorus ligands from the edge Re(I) complex units, which have the fac-[Re(N^N)(CO)₃(PR₂R')]⁺ structure, in linear-shaped Re(I) multinuclear complexes. This reaction was successfully applied to synthesize a novel precursor with ring-shaped multinuclear Re complexes (Re-rings) comprising different kinds of Re(I) units. The newly synthesized Re-rings, which consist of one Re unit with a 4,4'-bis(trifluoromethyl)-2,2'-bipyridine (CF₃bpy) ligand and one or two Re unit(s) with a 2,2'-bipyridine (bpy) ligand, showed almost quantitative excitation-energy harvesting ability from the Re unit(s) with bpy to that with CF₃bpy.