Photoreduction of 9,10-anthraquinone derivatives: transient spectroscopy and effects of alcohols and amines on reactivity in solution.

Abstract

The photoreduction of 9,10-anthraquinone (AQ), the 2-methyl, 2-ethyl, 2,3-dimethyl, 1,4-difluoro, 1-chloro and 1,8-dichloro derivatives as well as 1,4,4a,9a-tetrahydroanthraquinone, 1,2-benzanthraquinone and 6,13-pentacenequinone in nonaqueous solution at room temperature was studied by time-resolved UV-visible spectroscopy. Upon 308 nm excitation of AQ the triplet state reacts with alcohols and triethylamine (TEA). The rate constant of triplet quenching by amines is close to the diffusion-controlled limit. The semiquinone radical *QH/ Q*- is the main intermediate, and the half-life of the second-order decay kinetics depends significantly on the donor and the medium. Photoinduced charge separation after electron transfer from amines to the triplet state of AQ in acetonitrile and the subsequent charge recombination or neutralization also were measured by transient conductivity. The maximum quantum yield, lambdairr = 254 nm, of photoconversion into the strongly fluorescing 9,10-dihydroxyanthracenes is close to unity. The fluorescence with maximum at 460-480 nm and a lifetime of 20-30 ns disappears as a result of a complete recovery into AQ, when the dihydroxyanthracenes are exposed to oxygen. The mechanisms of photoreduction of parent AQ in acetonitrile by 2-propanol and in benzene and acetonitrile by TEA are discussed. The effects of AQ follow essentially the same pattern. The various functions of oxygen, e.g. (1) quenching of the triplet state; (2) quenching of the semiquinone radical, thereby forming HO2*/O2*- radicals; and (3) trapping of the dihydroxyanthracenes are outlined.