Understanding the photochemistry of a crystalline push-pull norbornadiene photoswitch.

Molecular solar thermal (MOST) materials store and release solar energy through light-induced reversible reactions involving molecular photoswitches. Solid-state crystalline MOST materials can offer higher energy densities and easier device integration than their liquid counterparts. However, their photochemical mechanisms remain poorly understood. Norbornadiene (NBD), which undergoes a [2 + 2]-photocycloaddition to form its photoisomer quadricyclane (QC), has been proposed as a candidate for MOST applications. We used multiconfigurational quantum mechanical calculations and non-adiabatic molecular dynamics to investigate the mechanism of a push-pull NBD-derivative, 1,5,6-trimethyl-2,3-dicyanonorbornadiene (TMDCNBD). This study demonstrates a cutting-edge multiscale ONIOM(QM/QM') nonadiabatic molecular dynamics framework in TMDCNBD crystals. The crystal packing of TMDCNBD preserves molecular flexibility, enabling ultrafast [2 + 2]-photocycloaddition via energetically accessible S 1/S 0 conical intersections, with negligible exciton transport. Simulations predict product quantum yields of 57% for TMDCNBD and 37% for its metastable quadricyclane (QC) form, TMDCQC, which stores 0.36 MJ kg-1. This work demonstrates push-pull norbornadiene photoswitches are promising crystalline MOST candidates and establishes a transferable computational protocol for modelling ultrafast photochemistry in the solid state.