Stabilization of Carbocation Intermediate by Cucurbit[7]uril Enables High Photolysis Efficiency

• DOI: 10.1021/acs.orglett.3c01854
• Publication Date: 2023-07-10T15:32:58Z
• Authors: Shan Mei; Qi Ou; Xingchen Tang; Jiang-Fei Xu; Xi Zhang
• Keywords: Heterolysis; Carbocation; Quantum yield

A cucurbit[7]uril-based host-guest strategy is employed to enhance the efficiency of photolysis reactions that release caged molecules from photoremovable protecting groups. The benzyl acetate follows a heterolytic bond cleavage mechanism, thereby leading formation contact ion pair as key reactive intermediate. Gibbs free energy lowered by 3.06 kcal/mol through stabilization cucurbit[7]uril, revealed DFT calculations, which results in 40-fold increase quantum yield reaction. This methodology also applicable chloride leaving group and diphenyl group. We anticipate this research presents novel improve involving active cationics, enriching field supramolecular catalysis.