Photo‐ and Thermal‐Induced Isomerization of Diels–Alder Adducts of Pentacene and TCNE

Herein we report the formation of the second-ring Diels–Alder adduct together with the central-ring adduct in a reaction of pentacene and tetracyanoethylene at room temperature. DFT calculations showed that the difference between the free energy of the two isomers is about 3.9 kcal/mol. Photo- and thermal-induced isomerization between the central-ring adduct and the second-ring adduct were studied in solution and in polymer films. In solution, the less-stable second-ring adduct can be converted into the more-stable central-ring adduct either thermally or photochemically, but the reverse transformation does not occur. In a polymer matrix, isomerization can be photochemically induced in both directions at different wavelengths, which results in a photoswitchable system. Formation of pentacene in the photochemical experiments was also observed, which supports an isomerization process involving a photo-retro-Diels–Alder reaction.

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