A smart post-synthetic route towards[Fe_(2)Co_(2)]molecular capsules with electron transfer and bidirectional switching behaviors

作     者：Lingyi Meng Yi-Fei Deng Shihao Liu Zhiping Zheng Yuan-Zhu Zhang Lingyi Meng;Yi-Fei Deng;Shihao Liu;Zhiping Zheng;Yuan-Zhu Zhang

作者机构：Department of ChemistrySouthern University of Science and Technology(SUSTech)Shenzhen518055China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2021年第64卷第8期

页      面：1340-1348页

核心收录：

学科分类：08[工学] 080501[工学-材料物理与化学] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 

基　　金：This work was supported by the National Natural Science Foundation of China(21671095 21901108) and start-up fund from SUSTech.We thank Dr.Bin Chen from Soochow University for UV-Vis-NIR measurements 

主　　题：cyanide capsule supramolecule post-modification electron transfer bidirectional switch 

摘      要：Aldehyde groups were intentionally equipped on the cyanide-bridged[Fe_(2)Co_(2)]square molecules:{[(Tp*)Fe(CN)_(3)Co(bpy^(CHO))_(2)]_(2)-[PF_(6)]_(2)}·4MeOH(1,Tp*=hydrotris(3,5-dimethylpyrazol-1-yl)borate;bpy^(CHO)=4-formyl-4′-methyl-2,2′-bipyridine),thus providing chemical-active windows for post-modification towards desired *** this contribution,by taking advantage of efficient Schiff-base condensation between the aldehyde-substituted bipyridine derivative(bpyCHO)and alkyl diamines(H_(2)N-(CH_(2))_(n)NH_(2)),two discrete[Fe_(2)Co_(2)]compounds{[(Tp∗)Fe(CN)_(3)Co(bpy^(C=N(CH_(2))_(n)N=C)bpy)]2[PF_(6)]_(2)}⋅6DMF(2,n=5;3,n=7)were prepared,where the cyanide-bridged[Fe_(2)Co_(2)]square cores were encapsulated by the flexible alkyl ***-temperature single-crystal X-ray diffraction and magnetic studies revealed complete thermo(T_(1/2)=233 K(2)and 237 K(3))and photo-induced electron transfer event accompanying spin transition between the diamagnetic[Fe^(Ⅱ)_(LS2)Co^(Ⅲ)_(LS2)]state and the paramagnetic[Fe^(Ⅲ)_(LS2)Co^(Ⅱ)_(HS2)]state(LS,low spin;HS,high spin).In addition,the bidirectional switching between the two states was achieved with alternating laser irradiation at 808 and 532 nm at 10 K.