Solar Energy Storage: Competition between Delocalized Charge Transfer and Localized Excited States in the Norbornadiene to Quadricyclane Photoisomerization,Journal of the American Chemical Society

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Solar Energy Storage: Competition between Delocalized Charge Transfer and Localized Excited States in the Norbornadiene to Quadricyclane Photoisomerization
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-12-27 , DOI: 10.1021/jacs.1c04322
Wiebke Alex ₁ , Patrick Lorenz ₁ , Christian Henkel ₁ , Timothy Clark ₁ , Andreas Hirsch ₁ , Dirk M Guldi ₁

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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.

中文翻译：

太阳能存储：降冰片二烯到四环烷光异构化中的离域电荷转移和局部激发态之间的竞争

我们首次描述了关于吸收红色的降冰片二烯 (NBDs) 到四环烷 (QCs) 的光异构化的完整反应坐标。我们的研究通过使用一系列时间分辨技术超越了稳态调查。重要的是，NBD 的红色吸收是通过不同的电荷转移特性实现的。调整其强度可以控制重排的光可逆性。在强电荷转移特性（弱吸电子酯和强给电子二甲基苯胺）的情况下，用可见光光照射 NBD 的离域电荷转移吸收可以可逆地提供 QC。形成鲜明的对比，进入 NBD 局部激发态的紫外光辐照会导致光致降解，并且在任何情况下都不能反异构化为 NBD。如果电荷转移特性较弱（弱吸电子酯和弱供电子苯基），则可见与光辐照光无关的可逆性。

更新日期：2022-01-12

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