Multiconfigurational photodynamics simulations reveal the mechanism of photodecarbonylations of cyclopropenones in explicit aqueous environments.

ABSTRACT: Gas-evolving photochemical reactions use light and mild conditions to access strained organic compounds irreversibly. Cyclopropenones are a class of light-responsive molecules used in bioorthogonal photoclick reactions; their excited-state decarbonylation reaction mechanisms are misunderstood due to their ultrafast (<100 femtosecond) lifetimes. We have combined multiconfigurational quantum mechanical (QM) calculations and non-adiabatic molecular dynamics (NAMD) simulations to uncover the excited-state mechanism of cyclopropenone and a photoprotected cyclooctyne-(COT)-precursor in gaseous and explicit aqueous environments. We explore the role of H-bonding with fully quantum mechanical explicitly solvated NAMD simulations for the decarbonylation reaction. The cyclopropenones pass through asy

SUBMITTER: Adrion DM 

PROVIDER: S-EPMC10664470 | biostudies-literature | 2023 Nov

REPOSITORIES: biostudies-literature