Solar energy storage reactions involving metal complexes

Abstract

-Photochemical properties of transition metal complexes are discussed as they relate to possible schemes for energy storage. Complexes of copper(I) with r-acceptor ligamds have been used to sensitize isomerizations of organic molecules, and there is room for considerable further investigation in this area. Electron transfer reactions have been more intensively studied. These reactions fall into three broad categories: ionization, oxidative addition/reductive elimination, and excited state electron transfer. Experiments in the first two categories have ierally led to rather poor storage efficiency and have required ultraviolet light. But long-lived excited states of coordination compounds can participate in chemical reactions with high efficiency, and such systems are promising for solar energy storage. Specific systems of this type that are discussed in detail involve electron transfer quenching of the lowest emissive excited states of Ru(2,2'_bipyridine), M (diisocyanoalkane) (M=Rh,Ir), and Mo6Cl.

Critical deactivating modes for the metal-2,2'-bipyridine or -1,10-phenanthroline MLCT excited states

“…24, No. 1,1985 Notes What did seem clear from the analysis is that no one mode, and in particular a mode with ho «1350 cm"1, corresponds to the observed displacements in reduction. Rather, contributions from at least three framework stretching modes (with ho = 1000-1600 cm"1) are required to approach a reasonable approximation to the displacements.…”

C−O Bond Fragmentation of 4-Picolyl- and N-Methyl-4-picolinium Esters Triggered by Photochemical Electron Transfer

“…Previous work has elucidated many of the factors that control the rates of these reactions. , Therefore, many current efforts are aimed at identifying and demonstrating useful applications of these processes. Applications include solar energy conversion, − photolithography, molecular electronics, , and the design of novel synthetic transformations. With regard to the latter, it has long been recognized that PET is capable of generating high-energy radical and radical ion pairs.…”

Direct rate measurements of the combination and disproportionation of vinyl radicals

“…Only in recent years has progress in understanding some aspects of the spectroscopy and gas-phase chemistry of vinyl radicals been reported. By use of either mass spectrometric detection or diode laser absorption techniques, gas-phase kinetic parameters for reactions of vinyl radicals with molecular and atomic oxygen, hydrogen, and HC1 have been investigated at low temperatures.1"5 (1) Slagle, I. R.; Park, J. Y.; Heaven, M. C.; Gutman, D. J. Am.…”