The rational design of aqueous-phase supramolecular catalysts that integrate substrate recognition,activation,reaction selectivity,and recyclability remains a significant challenge.This work presents a cucurbit[8]uril...The rational design of aqueous-phase supramolecular catalysts that integrate substrate recognition,activation,reaction selectivity,and recyclability remains a significant challenge.This work presents a cucurbit[8]uril(Q[8])-based supramolecular photocatalyst,TMV^(8+)@Q[8],which selectively encapsulates aromatic sulfide substrates via host-stabilized charge transfer(HSCT)interactions while markedly enhancing singlet oxygen(^(1)O_(2))generation.Under visible-light irradiation,the substrate-TMV8+@Q[8]system facilitates the efficient catalytic oxidation of aromatic sulfides to sulfoxides.Competitive displacement experiments confirm that product desorption is substrate-driven,enabling catalyst regeneration.Crucially,the Q[8]cavity plays a multifaceted role by enhancing substrate activation through HSCT,promoting^(1)O_(2)^(-)mediated oxidation via confinement effects,and enforcing selectivity through size exclusion.These findings establish a new paradigm for supramolecular photocatalysis,wherein macrocyclic confinement concurrently enhances substrate recognition,catalytic efficiency,and recyclability.This study thereby provides a strategic blueprint for designing enzyme-inspired supramolecular photocatalysts operable in aqueous media.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.22271090).
文摘The rational design of aqueous-phase supramolecular catalysts that integrate substrate recognition,activation,reaction selectivity,and recyclability remains a significant challenge.This work presents a cucurbit[8]uril(Q[8])-based supramolecular photocatalyst,TMV^(8+)@Q[8],which selectively encapsulates aromatic sulfide substrates via host-stabilized charge transfer(HSCT)interactions while markedly enhancing singlet oxygen(^(1)O_(2))generation.Under visible-light irradiation,the substrate-TMV8+@Q[8]system facilitates the efficient catalytic oxidation of aromatic sulfides to sulfoxides.Competitive displacement experiments confirm that product desorption is substrate-driven,enabling catalyst regeneration.Crucially,the Q[8]cavity plays a multifaceted role by enhancing substrate activation through HSCT,promoting^(1)O_(2)^(-)mediated oxidation via confinement effects,and enforcing selectivity through size exclusion.These findings establish a new paradigm for supramolecular photocatalysis,wherein macrocyclic confinement concurrently enhances substrate recognition,catalytic efficiency,and recyclability.This study thereby provides a strategic blueprint for designing enzyme-inspired supramolecular photocatalysts operable in aqueous media.
