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Solar Energy Storage: Competition between Delocalized Charge Transfer and Localized Excited States in the Norbornadiene to Quadricyclane Photoisomerization

2021; American Chemical Society; Volume: 144; Issue: 1 Linguagem: Inglês

10.1021/jacs.1c04322

1943-2984

Wiebke Alex, Patrick Lorenz, Christian Henkel, Timothy Clark, Andreas Hirsch, Dirk M. Guldi,

Radical Photochemical Reactions

We describe for the first time the full reaction coordinate regarding the photoisomerization of red-absorbing norbornadienes (NBDs) to quadricyclanes (QCs). Our studies go beyond steady-state investigations by using an arsenal of time-resolved techniques. Importantly, the red absorption of NBDs is made possible by a different charge-transfer character; adjusting its strength enables control over the photoreversibility of the rearrangement. In the case of strong charge-transfer character (a weakly electron-withdrawing ester and a strongly electron-donating dimethylaniline), photoirradiation with visible light into the delocalized charge-transfer absorption of NBD affords QC reversibly. In stark contrast, UV photoirradiation into the NBD localized excited state leads to a photoinduced degradation and cannot be back-isomerized to NBD under any circumstances. If the charge-transfer character is weak (a weakly electron-withdrawing ester and a weakly electron-donating phenyl), reversibility is seen independently of the photoirradiation light.