Photochemistry of Transition Metal ComplexesBased in part on the article Photochemistry of Transition Metal Complexes by Lisa McElwee‐White which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Abstract

Photochemistry has evolved into a powerful tool for the highly selective generation of reactive intermediates in inorganic and organometallic chemistry. This review examines the state of the art in the examination of mechanisms of photochemical reactions utilizing techniques such as frozen matrices and fast time‐resolved methods. The application of photochemistry to the preparation of dihydrogen, alkane, and noble gas intermediates is reviewed along with the significance of these intermediates in the understanding of the mechanism of oxidative addition processes. Experiment and theory of charge transfer phenomena are extensively discussed along with the application of these processes to semiconductor and biochemical studies. Applications of photocrystallography to the examination of linkage isomers and very short‐lived excited state species are reviewed. Finally, a number of examples of the application of photochemical reactions, such as the photolysis of Fisher carbene species to generate ketenelike intermediates, to synthesis are discussed. The literature is reviewed to the end of 2003.

Quantitative wave function analysis for excited states of transition metal complexes

“…Due to these properties, various classes of TMCs are actively employed, or show high potential, for a large number of innovative technological applications [1]. They are used in devices which convert solar energy, either directly to electrical current in dye-sensitized solar cells [2][3][4][5], to chemical energy of fuels in arti cial photosynthesis [6,7], or to complex chemicals in TMC-based photocatalysis [8][9][10]. Furthermore, TMCs are useful in photodynamic therapy [11][12][13], where light activates therapeutically bene cial chemical reactions that initiate apoptosis.…”

“…Furthermore, TMCs are useful in photodynamic therapy [11][12][13], where light activates therapeutically bene cial chemical reactions that initiate apoptosis. TMCs can also be used to produce light, either for illumination or display purposes in organic light-emitting diodes (OLEDs) [4,[14][15][16], or for various kinds of luminescent probes in biochemical research [9,[17][18][19], biological imaging [13,20], or sensoring [13]. Moreover, TMCs can also be used to modify light, by means of their non-linear optical properties [4,21] or photoswitching abilities [22,23].…”

“…Actually, most of the above-mentioned applications are based on achieving some favorable properties of particular excited states [16,29,30]. For example, redox photocatalysis exploits the fact that MLCT states can be both better electron acceptors and electron donors than the ground state [9]. TMC-based OLEDs rely on MLCT states which provide ultrafast excited-state dynamics-internal conversion (IC) and intersystem crossing (ISC)-and a long life time of the lowest excited state [15,16].…”