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Photochromism of phenoxynaphthacenequinones: diabatic or adiabatic phenyl group transfer?

Název česky Fotochromismus fenoxynaftacenchinonů: diabatický nebo adiabatický přenos?
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BORN R. FISCHER W. HEGER Dominik TOKARCZYK B. WIRZ Jakob

Rok publikování 2007
Druh Článek v odborném periodiku
Časopis / Zdroj PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES
Fakulta / Pracoviště MU

Přírodovědecká fakulta

Citace
Obor Jaderná a kvantová chemie, fotochemie
Klíčová slova LASER FLASH-PHOTOLYSIS; CONJUGATED RADICALS; ELECTRON-TRANSFER; PHOTOISOMERIZATION; MECHANISM; DERIVATIVES; SINGLET; STATE; 6-PHENOXY-512-NAPHTHACENEQUINONE; PHOTOCHEMISTRY
Popis The photochromic reactions of 6-phenyloxy-5,12-naphthacenequinone ( 1) and of the 6,11-diphenyloxy derivative 2 were investigated by subpicosecond pump-probe, photoacoustic, and emission spectroscopies, and by nanosecond laser. ash photolysis ( LFP). The transformation of the trans-quinones 1 and 2 to their ana-isomers proceeds via short-lived triplet states of 1 and 2 ( tau ca. 2 ns) and spiro-bridged biradical intermediates ( ca. 6 ns). The long-lived ( mu s) ana-triplets that are observed by LFP of 1 and 2 are formed ( predominantly) by reexcitation of the biradicals and ana-quinones, which appear during the laser pulse. The reverse reaction, ana -> trans, proceeds exclusively from the lowest pi, pi* singlet state of the ana-quinones.
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