Preparing enzyme-like artificial hosts that can undergomulti-stimuli-responsive deformationswhile simultaneously enhancing vip reactivity remains a challenge.Here,a flexible coordination tube 1 based on semirigid fo...Preparing enzyme-like artificial hosts that can undergomulti-stimuli-responsive deformationswhile simultaneously enhancing vip reactivity remains a challenge.Here,a flexible coordination tube 1 based on semirigid four-arm ligands was prepared that could undergo multi-stimuli-responsive deformations,including temperature-driven distortions,vip-tuning deformations(e.g.,distortion,contraction,and expansion),stepwise deformations caused by vip concentrations,specific deformations synergistically induced by vips and temperatures.Moreover,tube 1 could effectively regulate the reactivity of Z-stilbene and E/Z-azoarenes throughmutual induced-fit.Inside the tube,the photoisomerization rate and photoisomerization selectivity of Z-stilbene could be enhanced simultaneously,whereby the expansion of tube 1 and the distortion of Z-stilbene occurred synergistically.For the azoarenes in tube 1,E→Z photoisomerization,Z→E photoisomerization,and Z→E thermal isomerizationwere regulated,where Z→E isomerization tended to be promoted and E→Z isomerization was inhibited because E-isomers matched tube 1 better than Z-isomers.This work provides a useful strategy for synthesizing enzymelike artificial hosts.展开更多
基金supported by the National Key Research and Development Program of China(grant nos.2021YFA1500400 and 2018YFA0704500)the National Natural Science Foundation of China(grant no.22471267)+1 种基金the Natural Science Foundation of Fujian Province,China(grant no.2023J06046)the Selfdeployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences(grant no.CXZX-2022-GH06).
文摘Preparing enzyme-like artificial hosts that can undergomulti-stimuli-responsive deformationswhile simultaneously enhancing vip reactivity remains a challenge.Here,a flexible coordination tube 1 based on semirigid four-arm ligands was prepared that could undergo multi-stimuli-responsive deformations,including temperature-driven distortions,vip-tuning deformations(e.g.,distortion,contraction,and expansion),stepwise deformations caused by vip concentrations,specific deformations synergistically induced by vips and temperatures.Moreover,tube 1 could effectively regulate the reactivity of Z-stilbene and E/Z-azoarenes throughmutual induced-fit.Inside the tube,the photoisomerization rate and photoisomerization selectivity of Z-stilbene could be enhanced simultaneously,whereby the expansion of tube 1 and the distortion of Z-stilbene occurred synergistically.For the azoarenes in tube 1,E→Z photoisomerization,Z→E photoisomerization,and Z→E thermal isomerizationwere regulated,where Z→E isomerization tended to be promoted and E→Z isomerization was inhibited because E-isomers matched tube 1 better than Z-isomers.This work provides a useful strategy for synthesizing enzymelike artificial hosts.
