✍ Scribed by Antonı́n Vlček Jr.
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Metal-to-ligand charge-transfer (MLCT) excitation of organometallic and coordination complexes has diverse chemical and physical consequences, depending on the molecular structure and the medium. It can promptly start an ultrafast ligand dissociation, populate a long-lived, charge-separated, 3MLCT state that shows typical reactivity of the oxidised metal atom or reduced ligand (electron transfer, associative substitution, oxidative addition), or lead to a long-lived 3MLCT state from which another, more reactive, excited state is populated thermally. Alternatively, a MLCT state may be unreactive with respect to the breaking or formation of metal-ligand bonds but engaged in electron-or energy-transfer reactions or just decaying to the ground state. The MLCT photochemistry is discussed in terms of the bonding properties and dynamics of the MLCT excited states which are, to some extent, dependent on interactions with other excited states of different orbital origins (LF, |y*, IL). An examination of actual mechanistic roles of MLCT states in representative classes of photochemical reactions allows to outline more general relations between the molecular structure and photoreactivity of MLCT-active organometallic compounds.
📜 SIMILAR VOLUMES
The photoreactivity of coordination compounds in a MLCT excited state can be attributed to the nature of the oxidized metal and/or the reduced ligand. The general features of such photoreactions have been recently reviewed (A. Vogler, H. Kunkely, Coord. Chem. Rev. 177 (1998) 81). The present report