Mono- and dinuclear complexes of tricarbonylrhenium(I) with 4-methyl-2,2′-bipyridine-4′-carbonitrile

Juan H. Mecchia Ortiz, Faustino E. Morán Vieyra, Claudio D. Borsarelli, Isabel Romero, Xavier Fontrodona, Teodor Parella, Noemí D. Lis De Katz, Florencia Fagalde, Néstor E. Katz

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    5 Citations (Scopus)

    Abstract

    Novel mono- and dinuclear tricarbonylrhenium(I) complexes of formula [Re(Mebpy-CN)(CO)3Cl] (1), [Re(Mebpy-CN)(CO)3(CH 3CN)](PF6) (2), and [(CH3CN)(CO) 3Re(Mebpy-CN)Ru(NH3)5](PF6) 3 (3), in which 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 owing to the nitrile substituent increases the emission quantum yields of the 3MLCT (metal-to-ligand charge-transfer) lowest-lying excited states of 1 and 2 with respect to the corresponding bpy complexes (bpy = 2,2′-bipyridine). The mixed-valent species of formula [(CH 3CN)(CO)3Re(Mebpy-CN)Ru(NH3)5] 4+ (4) was prepared in situ and as a mixed salt; the charge recombination from its metal-to-metal charge-transfer (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. Mono- and dinuclear tricarbonylrhenium(I) complexes of formula [Re(Mebpy-CN)(CO)3Cl] (1; Mebpy-CN = 4-methyl-2,2′-bipyridine-4′-carbonitrile), [Re(Mebpy-CN)(CO)3(CH3CN)](PF6) (2), [(CH 3CN)(CO)3Re(Mebpy-CN)Ru(NH3) 5](PF6)3 (3), and [(CH3CN)(CO) 3Re(Mebpy-CN)Ru(NH3)5]4+ (4) were prepared and characterized by spectroscopic, photophysical, and computational techniques. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Original languageEnglish
    Pages (from-to)3359-3369
    JournalEuropean Journal of Inorganic Chemistry
    Issue number21
    DOIs
    Publication statusPublished - 1 Jan 2014

    Keywords

    • Coordination chemistry
    • Density functional calculations
    • Electron transfer
    • Rhenium
    • Ruthenium

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