A Complete Unveiling of the Mechanism and Chirality in Photoisomerization of Arylazopyrazole 3pzH: Combined Electronic Structure Calculations and AIMS Dynamic Simulations.

The arylazopyrazole 3pzH as a novel photoswitch exhibits quantitative switching and high thermal stability. In this work, combined electronic structure calculations and ab initio multiple spawning (AIMS) dynamic simulations were performed to systemically investigate the cis ↔ trans photoisomerization mechanism and the chiral preference after photoexcitation of 3pzH to the first excited singlet state (S 1 ). Unlike most of the azoheteroarene photoswitches reported previously, many twisted and T-shaped cis isomers were found to be stable for 3pzH in the S 0 state, owing to the moderate interaction between the hydrogen atom and π electrons of the aromatic ring. Two twisted cis isomers with different chirality (( M )-Z 1 and ( P )-Z 1 ), the most stable T-shaped cis isomer (( T )-Z 2 ), and the most stable planar trans isomer (E 2 ) were selected as the initial structures to carry out the AIMS nonadiabatic dynamic simulations. Following excitation to the S 1 state, all of the cis isomers decayed to conical intersection (CI) regions via the same bicycle pedal mechanism, while the evolution of the trans isomers to their CI regions was achieved via rotation around the N═N bond. More importantly, chiral preferences were found for the twisted cis isomers in the S 1 state through the AIMS dynamic simulations due to the steric effect and static electronic repulsion. Notably, chirality was also observed in S 1 isomerization starting from the planar E 2 isomer because of the dynamic effect. After the nonadiabatic transition to the S 0 state, the bicycle pedal mechanism was found to play a crucial role in cis ↔ trans photoisomerization. The simulated photoisomerization productivities were generally consistent with past experimental observations. Our calculations not only uncover the underlying reason for the excellent photoswitching properties of 3pzH but also enrich the knowledge of photoisomerization for azoheteroarene photoswitches, which will surely benefit their rational design.