Chemical transformations are fundamentally governed by electron redistribution during bond reorganization. While conventional strategies exploit thermal, optical, mechanical, or electrical energy to steer reactivity, ...Chemical transformations are fundamentally governed by electron redistribution during bond reorganization. While conventional strategies exploit thermal, optical, mechanical, or electrical energy to steer reactivity, elucidating electron behavior at the quantum level remains central to catalyst design and mechanistic elucidation.展开更多
Photoreactive coordination polymers are important platforms for the implementation of tailored solidstate photochemical reactions.These crystalline compounds can also be employed as photo-controlled intelligent materi...Photoreactive coordination polymers are important platforms for the implementation of tailored solidstate photochemical reactions.These crystalline compounds can also be employed as photo-controlled intelligent materials for the design and manufacture of advanced devices.Herein,a comb-like photoreactive coordination polymer,formulated as{[Zn(5-Cl-1,3-bdc)(H_(2)O)(2,3-ppe)]·H_(2)O}_(n)(1),was prepared based on the hydrothermal reaction between Zn(NO_(3))2·6H_(2)O,5-chlorobenzene-1,3-dicarboxylic acid(5-Cl-1,3-H_(2)BDC)and 1-(2-pyridyl)-2-(3-pyridyl)-ethylene(2,3-ppe).Upon irradiation with sunlight,the 1H NMR spectroscopy,UV-vis absorption spectroscopy and single crystal X-ray diffraction analyses results indicated that 1 can undergo a[^(2+)2]photocycloaddition reaction and thus generate a unique ladder-like coordination chain{[Zn(5-Cl-1,3-bdc)(H_(2)O)(2,3-bpbpcb)_(0.5)]·H_(2)O}n(1a,2,3-bpbpcb=1,3-bis(2-pyridyl)-2,4-bis(3-pyridyl)cyclobutane)via single-crystal to single-crystal(SCSC)transformation.Upon irradiation of UV light with a wavelength of 254 nm,the newly formed coordination chain 1a can undergo a reversible cycloreversion reaction and return to 1.The reversible photo-controllable cycloaddition-cycloreversion reaction between 1 and 1a also exhibits an interesting behavior of photo-switchable fluorescence.The reversible structural transformation and fluorescence switching behavior of 1 make it a potential photo-controlled intelligent material for optical information storage,optical anti-counterfeiting,fluorescence sensors and other fields.展开更多
文摘Chemical transformations are fundamentally governed by electron redistribution during bond reorganization. While conventional strategies exploit thermal, optical, mechanical, or electrical energy to steer reactivity, elucidating electron behavior at the quantum level remains central to catalyst design and mechanistic elucidation.
基金supported by the National Natural Science Foundation of China(21201068)the Major Projects of Natural Science Research in Universities of Jiangsu Province(20KJA150002)+2 种基金the Natural Science Research Program of Huaian Science and Technology Bureau(HAB202156)the Huaishang Talent Program of Huaian,the Open Project of Key Laboratory for Chemistry of Low-Dimensional Materials in Universities of Jiangsu Province(Grant JSKC24027)the Excellent Scientific and Technological Innovation Team of Advanced Energy Materials Chemistry in Universities of Jiangsu Province and the Innovative Training Program for College Students.
文摘Photoreactive coordination polymers are important platforms for the implementation of tailored solidstate photochemical reactions.These crystalline compounds can also be employed as photo-controlled intelligent materials for the design and manufacture of advanced devices.Herein,a comb-like photoreactive coordination polymer,formulated as{[Zn(5-Cl-1,3-bdc)(H_(2)O)(2,3-ppe)]·H_(2)O}_(n)(1),was prepared based on the hydrothermal reaction between Zn(NO_(3))2·6H_(2)O,5-chlorobenzene-1,3-dicarboxylic acid(5-Cl-1,3-H_(2)BDC)and 1-(2-pyridyl)-2-(3-pyridyl)-ethylene(2,3-ppe).Upon irradiation with sunlight,the 1H NMR spectroscopy,UV-vis absorption spectroscopy and single crystal X-ray diffraction analyses results indicated that 1 can undergo a[^(2+)2]photocycloaddition reaction and thus generate a unique ladder-like coordination chain{[Zn(5-Cl-1,3-bdc)(H_(2)O)(2,3-bpbpcb)_(0.5)]·H_(2)O}n(1a,2,3-bpbpcb=1,3-bis(2-pyridyl)-2,4-bis(3-pyridyl)cyclobutane)via single-crystal to single-crystal(SCSC)transformation.Upon irradiation of UV light with a wavelength of 254 nm,the newly formed coordination chain 1a can undergo a reversible cycloreversion reaction and return to 1.The reversible photo-controllable cycloaddition-cycloreversion reaction between 1 and 1a also exhibits an interesting behavior of photo-switchable fluorescence.The reversible structural transformation and fluorescence switching behavior of 1 make it a potential photo-controlled intelligent material for optical information storage,optical anti-counterfeiting,fluorescence sensors and other fields.
