6533b836fe1ef96bd12a098e

RESEARCH PRODUCT

Supramolecular Construction of Cyanide-Bridged Re I Diimine Multichromophores

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The reactions of labile [Re(diimine)(CO)3(H2O)]+ precursors (diimine = 2,2′-bipyridine, bpy; 1,10-phenanthroline, phen) with dicyanoargentate anion produce the dirhenium cyanide-bridged compounds [{Re(diimine)(CO)3}2CN)]+ (1 and 2). Substitution of the axial carbonyl ligands in 2 for triphenylphosphine gives the derivative [{Re(phen)(CO)2(PPh3)}2CN]+ (3), while the employment of a neutral metalloligand [Au(PPh3)(CN)] affords heterobimetallic complex [{Re(phen)(CO)3}NCAu(PPh3)]+ (4). Furthermore, the utilization of [Au(CN)2]−, [Pt(CN)4]2–, and [Fe(CN)6]4–/3– cyanometallates leads to the higher nuclearity aggregates [{Re(diimine)(CO)3NC}xM]m+ (M = Au, x = 2, 5 and 6; Pt, x = 4, 7 and 8; Fe, x = 6, 9 and 10). All novel compounds were characterized crystallographically. Assemblies 1–8 are phosphorescent both in solution and in the solid state; according to the DFT analysis, the optical properties are mainly associated with charge transfer from Re tricarbonyl motif to the diimine fragment. The energy of this p...