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UV Photochemistry of the Energy-Storing Isomer of a Norbornadiene-Based Molecular Switch: Ring Opening; Rehybridised Intramolecular Charge Transfer; and Isomerisation into a Carbene Photoproduct
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DOI：10.1039/D6CP01643J.png)
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Abstract
En 中文
Photoswitches based on the norbornadiene-quadricyclane (NBD-QC) isomer pair capture solar energy by undergoing the NBD → QC photoisomerisation reaction. The energy-storing QC isomer contains two highly strained three-membered rings; which implies that it may be susceptible to photodegradation through exposure to the ultraviolet (UV) component of sunlight. In the present study; we use nonadiabatic molecular dynamics simulations to investigate the UV-induced photochemistry of the QC isomer of a representative NBD-QC photoswitch with a push-pull substitution motif. A pattern recognition algorithm is employed to analyze and systematize the simulation results. We find that the predominant outcome of UV absorption; observed in 75 out of the 100 simulated trajectories; is the opening of the four-membered ring which belongs to the QC moiety; although in about half of the trajectories which follow this relaxation pathway; the ring promptly closes again. However; in a small fraction of trajectories; the QC moiety instead breaks up; leading to the formation of a carbene photoproduct. We hypothesize that that the breakup of the QC moiety is the first step in a reaction pathway which leads to the decomposition of the photoswitch.
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