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期刊论文
resonance Raman Spectra and Photophysical Properties of Ruthenium Complexes with the 3,3'-Bipyridazine Ligand
J. Phys. Chem. A 2003, 107, 351-357,-0001,():
This report documents the spectroscopic and photophysical properties of the complexes, Ru(bpdz)32+ and [Ru(bpy)2(bpdz)]2+, where bpdz=3,3'-bipyridazine and bpy=2,2'-bipyridine Specifically, the complexes were characterized by UV-visible, emission, resonance Raman(RR), and transient resonance Raman (TR3) spectroscopic data, as well as lifetime measurements. The RR spectrum of the Ru(bpdz)32+ complex documents the characteristic modes of the coordinated ligand, whereas the RR spectra of the heteroleptic complex, [Ru(bpy)2(bpdz)]2+, obtained at judiciously chosen excitation wavelengths, reveal aelective enhancement of eithe bpy modes or bpdz modes, depending upon the particular excitation wavelength, permitting difinitive assignment of the observed, electronic absorption bands and establishing the lowest energy electroic transition as having a Ru-to-bpdz charge-transfer character. The TR3 spectrum of the Ru(bpdz)32+ complex reveals the characteristic frequencies of the coordinated bpdz-* anion radical, as expected, whereas corresponding studies of the heteroleptic com plex, [Ru(bpy)2(bpdz)]2+, reveal thee characteristic bpdz-* modes in the absence of any modes attributable to bpy-* anion radicals, providing difinitive evidence for the [Ru(III)(bpy)2(bpdz-*)]2+ formulation of the excited state of this com plex, Lifetime measurements for both com plexes, made over a wide, range of temperatures and interpreted with a model derived from previous measurements made on a large number of similar complexes, indicate that the two complexes of interest decay by different nonradiative pathways resulting from thermal population of a ligand field3dd and/or a lower lying 4th 3 MLCT state.
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