Synthesis, Structures, and Photoluminescent Properties of Tricyanidonitridorhenium(V) Complexes with Bipyridine-Type Ligands.
Inorg Chem
; 59(8): 5497-5508, 2020 Apr 20.
Article
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| MEDLINE
| ID: mdl-32271014
ABSTRACT
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 dxy orbital of the rhenium and π* orbitals of the bpy-type ligand, respectively.
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Colección:
01-internacional
Base de datos:
MEDLINE
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En
Revista:
Inorg Chem
Año:
2020
Tipo del documento:
Article
País de afiliación:
Japón