Li Ni-Ya, Liu Dong, Ren Zhi-Gang, Lollar Christina, Lang Jian-Ping, Zhou Hong-Cai
College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215123, P. R. China.
College of Chemistry and Materials Science, Huaibei Normal University , Huaibei 235000, P. R. China.
Inorg Chem. 2018 Jan 16;57(2):849-856. doi: 10.1021/acs.inorgchem.7b02817. Epub 2018 Jan 2.
The observation of a reversible chemical transformation corresponding to an external stimulus in the solid state is intriguing in the exploration of smart materials, which can potentially be applied in molecular machines, molecular switches, sensors, and data storage devices. The solid-state photodimerization reaction of 1,3-bis[2-(4-pyridyl)ethenyl]benzene (1,3-bpeb) in a one-dimensional coordination polymer {[Cd(1,3-bpeb)(4-FBA)]·HO} (4-FBA = 4-fluorobenzoate) with 365 nm UV light afforded syn-tetrakis(4-pyridyl)-1,2,9,10-diethano[2.2]metacyclophane (syn-tpmcp) in quantitative yield via a single-crystal-to-single-crystal (SCSC) transformation. Upon irradiation with 254 nm UV light, an SCSC conversion from syn-tpmcp to 1,3-bpeb was also achieved in quantitative yield within the syn-tpmcp-supported coordination polymer {[Cd(syn-tpmcp)(4-FBA)]·HO}. In particular, accompanied by the reversible transformation between 1,3-bpeb and syn-tpmcp, the coordination chain exhibits photocontrollable fluorescence-switching behavior, which makes this intelligent material an appealing candidate for practical applications.
在固态中观察到与外部刺激相对应的可逆化学转变，这在智能材料的探索中很有趣，这类材料有可能应用于分子机器、分子开关、传感器和数据存储设备。1,3-双[2-(4-吡啶基)乙烯基]苯(1,3-bpeb)在一维配位聚合物{[Cd(1,3-bpeb)(4-FBA)]·H₂O}(4-FBA = 4-氟苯甲酸酯)中，用365 nm紫外光进行固态光二聚反应，通过单晶到单晶(SCSC)转变以定量产率得到顺式四(4-吡啶基)-1,2,9,10-二亚乙基[2.2]间环环戊烷(syn-tpmcp)。在用254 nm紫外光照射时，在由syn-tpmcp支撑的配位聚合物{[Cd(syn-tpmcp)(4-FBA)]·H₂O}中也实现了从syn-tpmcp到1,3-bpeb的SCSC转化，且产率定量。特别地，伴随着1,3-bpeb和syn-tpmcp之间的可逆转变，配位链表现出光控荧光开关行为，这使得这种智能材料成为实际应用中一个有吸引力的候选者。
