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Photochromism of phenoxynaphthacenequinones: diabatic or adiabatic phenyl group transfer

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Abstract

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 flash 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 (tca. 2 ns) and spiro-bridged biradical intermediates (ca. 6 ns). The long-lived (μs) 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 p,p* singlet state of the ana-quinones.

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Authors and Affiliations

  1. Departement Chemie der Universität Basel, Klingelbergstrasse 80, 4056, Basel, Switzerland

    Reto Born, Dominik Heger, Bogdan Tokarczyk & Jakob Wirz

  2. Ciba Specialty Chemicals Inc., 4002, Basel, Switzerland

    Walter Fischer

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  1. Reto Born
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Correspondence to Jakob Wirz.

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Born, R., Fischer, W., Heger, D. et al. Photochromism of phenoxynaphthacenequinones: diabatic or adiabatic phenyl group transfer. Photochem Photobiol Sci 6, 552–559 (2007). https://doi.org/10.1039/b618661k

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