Machine learning photodynamics reveal intersystem-crossing-driven ladderdiene ring opening.

ABSTRACT: Photochemical ring-opening reactions have become an essential tool for chemical syntheses under mild conditions with high atom economy. We propose a near-visible light-induced electrocyclic ring-opening reaction to afford cyclooctatetraene (COT) using carbonyl-functionalized tricyclooctadiene (1) based on our machine learning (ML) accelerated photodynamics simulations. Our CAM-B3LYP/cc-pVDZ calculations show that carbonyl group reduce the S₁-energy of 1 to 3.65 eV (340 nm) from 6.25 eV, approaching the visible light range. The multiconfigurational CASSCF(12,11)/ANO-RCC-VDZP calculations show small S₁ and T₁ energy gaps near an S₁-minimum region. Our ML-photodynamics simulations with 1000 FSSH trajectories revealed a stepwise ring-opening mechanis

SUBMITTER: Li Z 

PROVIDER: S-EPMC12177735 | biostudies-literature | 2025 Jul

REPOSITORIES: biostudies-literature