Mono- and Dinuclear Complexes of Tricarbonylrhenium(I) with 4-Methyl-2,2′-bipyridine-4′-carbonitrile

J.H. MECCHIA ORTIZ; F.E. MORÁN VIEYRA; C. D. BORSARELLI; I. ROMERO; X. FRONTRODONA; T. PARELLA; N.D. L. DE KATZ; F. FAGALDE; N. KATZ

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY

WILEY-V C H VERLAG GMBH

Lugar: Weinheim; Año: 2014 p. 3359 - 3369

1434-1948

Novel mono- and dinuclear tricarbonylrhenium(I) complexes of formula [Re(MebpyCN)(CO)3Cl], 1, [Re(Mebpy-CN)(CO)3 (CH3CN)](PF6), 2, and [(CH3CN)(CO)3Re(Mebpy-CN) Ru(NH3)5](PF6)3, 3, with Mebpy-CN = 4-methyl-2,2?-bipyridine-4?-carbonitrile, were prepared and characterized by spectroscopic,photophysical and computational techniques. The complete structure of complex 2 was determined by X-ray diffraction. The increased conjugation in the bipyridyl ring due to the nitrile substituent increases the emission quantum yields of the 3MLCT lowest-lying excited states of 1 and 2 respect to the correspondingbpy complexes, with bpy = 2,2?-bipyridine. The mixed-valent species of formula [(CH3CN)(CO)3Re(Mebpy-CN)Ru(NH3)5]4+ ,4, was prepared in situ and as a mixed salt; the charge recombination from its MMCT excited state is predicted to lie in the Marcus inverted region. The electronic structures and optical properties of all the reported complexes calculated by DFT and TD-DFT methods agree reasonably well with experimental results.