2009: Photochemistry of Anthracene-9,10-endoperoxide

Fidder, H; Lauer, A; Freyer, W; Koeppe, B; Heyne, K

JOURNAL OF PHYSICAL CHEMISTRY A 2009, 113(22), p. 6289-6296

The wavelength dependence of the photochemistry of anthracene-9,10-endoperoxide (APO) in acetonitrile was quantitatively investigated at 5° C, with excitation varied from 240 to 450 nm. Anthracene (AC) and a diepoxide (DE) were identified as the main primary photoproducts. After short exposure times DE was at all wavelengths the dominating photoproduct, while AC was only formed for l<= 320 nm. The maximum AC quantum yield of 29% was reached at 270 nm. Anthraquinone (AQ) and a bicyclic acetal (BA) were identified as the main secondary products. Formation of AQ and BA occurred both from DE and from ground-state APO. Formation of BA from ground-state APO involved excited DE or BA itself, while formation of BA from DE required UV excitation of DE. Room-temperature thermolysis of APO only produced AQ. For l<= 310 nm the total photochemistry quantum yield was, within error margins, constant and close to unity. Between 300 and 450 nm, the tail of the APO absorption spectrum, a more or less monotonic decrease of the total photochemistry quantum yield was observed.


DOI 10.1021/jp901073s