Effect of delocalization and rigidity in the acceptor ligand on MLCT excited-state decay

Treadway, Joseph A., Loeb, Barbara, Lopez, Rosa, Anderson, Peter A., Keene, F. Richard, and Meyer, Thomas J. (1996) Effect of delocalization and rigidity in the acceptor ligand on MLCT excited-state decay. Inorganic Chemistry, 35 (8). pp. 2242-2246.

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Abstract

In its most simple form, the energy gap law for excited-state nonradiative decay predicts a linear dependence of ln knr on the ground- to excited-state energy gap, where knr is the rate constant for nonradiative decay. At this level of approximation, the energy gap law has been successfully applied to nonradiative decay in a wide array of MLCT excited states of polypyridyl complexes of ReI, RuII, and OsII. This relationship also predicts a dependence of knr on the structural characteristics of the acceptor ligand. We report here a brief survey of the literature which suggests that such effects exist and have their origin in the extent of delocalization of the excited electron in the ligand π* framework and on acceptor ligand rigidity.

Item ID: 22829
Item Type: Article (Refereed Research - C1)
Keywords: energy-gap law; photoinduced electron-transfer; resolved resonance; raman; tris-chelate complexes; transition-metal complexes; emission; spectral profiles; transfer absorption-band; ruthenium(ii) complexes; polypyridyl complexes; temperature-dependence
ISSN: 1520-510X
Date Deposited: 09 Aug 2012 23:48
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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