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Tricyanidonitridorhenium(V) complexes
with 2,2′-bipyridine
(bpy) derivatives in which the 4 and 4′ positions were substituted
by X, [ReN(CN)3(X2bpy)]− (X
= NMe2, NH2, OMe, Me, Cl, and Br), were newly
synthesized and characterized. The structures of the new complexes
were determined by single-crystal X-ray analysis. UV–vis spectra
of the complexes in dimethyl sulfoxide (DMSO) showed that the peak
maximum wavelengths of rhenium-to-π* bpy-type-ligand charge
transfer were in the range of 474–542 nm. Cyclic voltammograms
in n-(C4H9)4NPF6–DMSO showed one-electron oxidation and reduction waves
corresponding to the Re(VI/V) and X2bpy0/– processes, respectively. The new complexes and [ReN(CN)3bpy]− showed photoluminescence in the crystalline
phase at 295 and 80 K and in DMSO at 295 K. The origin of the emission
in DMSO was attributed to the triplet nature of the rhenium-to-π*
bpy-type-ligand charge-transfer transition. Density functional theory
calculations showed that the highest occupied and lowest unoccupied
molecular orbitals were primarily localized on the d
xy
orbital of the rhenium and π* orbitals of the bpy-type
ligand, respectively.
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