Journal of Physical Chemistry, Vol.100, No.42, 16786-16788, 1996
Rigid Rodlike Dinuclear Ru/Os Complexes of a Novel Bridging Ligand - Intercomponent Energy and Electron-Transfer Processes
The PF6- sails of the dinuclear complexes [(bpy)(2)Ru(PAP)Ru(bpy)(2)](4+) (Ru(II)PAPRu(II)), [(bpy)(2)Os(PAP)Os (bpy)(2)](4+) (Os(II)PAPOs(II)), and [(bpy)(2)Ru(PAP)Os(bpy)(2)](4+) (Ru(II)PAPOs(II)) have been prepared, where bpy 2,2’-bipyridine and PAP is a rodlike bridging ligand made of an adamantane-based spacer collinear with the coordination axis of two 1,10-phenanthroline units. In the prepared complexes, the metal-metal distance is 2.1 nm. In the Ru(II)PAPOs(II) compound, photoinduced energy transfer from the Ru-II-based to the Os-II-based unit takes place with rate constant 5.2 x 10(7) s(-1) at room temperature and 2.4 x 10(7) s(-1) al 77 K. In the mixed-valence Ru(II)PAPOs(III) compound, the luminescent excited stale of the Ru-II-based unit is quenched via electron transfer by the Os-III-based unit with rate constant 7.2 x 10(6) s(-1). The rate constant fur the back-electron-transfer reaction is 8.3 x 10(3) s(-1).
Keywords:TERPYRIDINE-TYPE COMPLEXES;LUMINESCENCE PROPERTIES;ELECTROCHEMICAL-BEHAVIOR;ABSORPTION-SPECTRA;EXCITED-STATES;PHOTOPHYSICAL PROPERTIES;BINUCLEAR COMPLEXES;CHARGE-TRANSFER;ROD-LIKE;PHOTOCHEMISTRY