The visible light-driven photoswitches are attracting widespread attention,but it is challenging to leverage their phototriggered structural changes to regulate dynamic bonds,assemblies,and materials.Herein,we incorpo...The visible light-driven photoswitches are attracting widespread attention,but it is challenging to leverage their phototriggered structural changes to regulate dynamic bonds,assemblies,and materials.Herein,we incorporated reversible covalent sites of aldehyde ring-chain tautomers into all-visible-light azobenzenes toward a versatile platform for light-controlled formation/exchange of dynamic C—N bonds from secondary amines.The movement of ring-chain equilibrium was attained via manipulating intramolecular multiple hydrogen bonding from E/Z configurational isomers.Such structural regulation further enabled photocontrolled kinetics for the formation and exchange reactions of cyclic hemiaminal ethers from secondary amines exhibiting kinetic rate reversal from E/Z isomers.The varied capability of E/Z configurational isomers in engaging in multiple hydrogen bonds of azo attached carboxylate with ammonium salt accounts for the difference.Moreover,the photoswitching performance of azobenzenes in different solutions was readily regulated by dynamic covalent reactions with amines.The dynamic reactivity control with visible light and associated mechanistic foundation add into the collection of photoswitchable dynamic covalent chemistry and would lay the foundation for subsequent biological and material applications.展开更多
Light-induced recognition,assemblies,and materials are intensive areas of research due to their high spatiotemporal resolution.Herein,we demonstrated photoswitchable molecular recognition via dithienylethene-triggered...Light-induced recognition,assemblies,and materials are intensive areas of research due to their high spatiotemporal resolution.Herein,we demonstrated photoswitchable molecular recognition via dithienylethene-triggeredreversible structural regulation of dynamic covalent hydrazone bonds.By combining dithienylethenes and cyclic hemiacetals,the photochemical open-ring and closed-ring forms enabled turningoff and on the creation of awide range of hydrazones when desired.Light-induced bidirectional switching between hydrazones and their cyclization structures promoted by a neighboring carboxyl group was further achieved.By taking advantage of reversible structural changes totoggleon andoff the binding pocket,photoswitchable recognitionofmetal ionswas realized.Finally,the construction of an acylhydrazone polymer offered a facile way for light-mediated selective extraction/release.The strategies and results reported here should find applications in many contexts,such asdynamicassemblies,molecular switches,and smart materials.展开更多
基金NSFC(S(92156010,22071247,22471274,and 22401279)the Key Research Program of Frontier Sciences(QYZDB-SSW-SLHO3O)of CAS+1 种基金the Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(GZC20241725)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZR112)for funding.
文摘The visible light-driven photoswitches are attracting widespread attention,but it is challenging to leverage their phototriggered structural changes to regulate dynamic bonds,assemblies,and materials.Herein,we incorporated reversible covalent sites of aldehyde ring-chain tautomers into all-visible-light azobenzenes toward a versatile platform for light-controlled formation/exchange of dynamic C—N bonds from secondary amines.The movement of ring-chain equilibrium was attained via manipulating intramolecular multiple hydrogen bonding from E/Z configurational isomers.Such structural regulation further enabled photocontrolled kinetics for the formation and exchange reactions of cyclic hemiaminal ethers from secondary amines exhibiting kinetic rate reversal from E/Z isomers.The varied capability of E/Z configurational isomers in engaging in multiple hydrogen bonds of azo attached carboxylate with ammonium salt accounts for the difference.Moreover,the photoswitching performance of azobenzenes in different solutions was readily regulated by dynamic covalent reactions with amines.The dynamic reactivity control with visible light and associated mechanistic foundation add into the collection of photoswitchable dynamic covalent chemistry and would lay the foundation for subsequent biological and material applications.
基金supported by National Natural Science Foundation of China(grant nos.22071247,92156010,22101283,and 22101284)the Strategic Priority Research Program(grant no.XDB20000000)+1 种基金the Key Research Program of Frontier Sciences(grant no.QYZDBSSW-SLH030)of the Chinese Academy of Sciences,Natural Science Foundation of Fujian Province(grant nos.2020J06035 and 2022J05085)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(grant no.2021ZR112).
文摘Light-induced recognition,assemblies,and materials are intensive areas of research due to their high spatiotemporal resolution.Herein,we demonstrated photoswitchable molecular recognition via dithienylethene-triggeredreversible structural regulation of dynamic covalent hydrazone bonds.By combining dithienylethenes and cyclic hemiacetals,the photochemical open-ring and closed-ring forms enabled turningoff and on the creation of awide range of hydrazones when desired.Light-induced bidirectional switching between hydrazones and their cyclization structures promoted by a neighboring carboxyl group was further achieved.By taking advantage of reversible structural changes totoggleon andoff the binding pocket,photoswitchable recognitionofmetal ionswas realized.Finally,the construction of an acylhydrazone polymer offered a facile way for light-mediated selective extraction/release.The strategies and results reported here should find applications in many contexts,such asdynamicassemblies,molecular switches,and smart materials.
