一例具有可逆热诱导电荷转移行为的二维氰基桥联W^(Ⅴ)-Co^(Ⅱ)配合物  

A 2D cyano-bridged W^(Ⅴ)-Co^(Ⅱ)coordination network exhibiting reversible thermal-induced charge transfer

作　　者：刘丹[1] 赵亮[1] 邵震 孟银杉 刘涛[1] LIU Dan;ZHAO Liang;SHAO Zhen;MENG Yin-Shan;LIU Tao(State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian,Liaoning 116024,China)

机构地区：[1]大连理工大学,精细化工国家重点实验室,大连116024

出　　处：《无机化学学报》2023年第2期367-374,共8页Chinese Journal of Inorganic Chemistry

基　　金：financially supported by the National Natural Science Foudation of China(Grants No.22103009,22025101,22222103,22173015,21871039,21801037,91961114,and 22071017);financial support by the Fundamental Research Funds for the Central Universities of China(Grants No.PA2021GDSK0063 and PA2020GDJQ0028)。

摘　　要：具有不同自旋态的磁性双稳态材料因在存储器件和分子开关领域具有广泛的应用前景而备受关注。本文报道了一种基于W^(Ⅴ)-Co^(Ⅱ)电荷转移过程的新型磁性双稳态化合物。通过将4-((2-萘-1-基)乙烯基)吡啶(4-nvp)引入氰基桥接的W^(Ⅴ)-Co^(Ⅱ)层框架中,合成了一例氰基桥联二维双金属网络配合物{[W^(Ⅴ)(CN)_(8)]_(2)[Co^(Ⅱ)(4-nvp)_(4)]_(3)}·4CH_(3)OH(1),其中辅助配体4-nvp可以提供分子内和分子间π-π相互作用。磁性研究结果表明,化合物1表现出可逆的电子转移耦合诱导自旋转变行为(ETCST)。该过程使体系自旋态由W^(Ⅴ)—CN—Co^(Ⅱ)_(HS)(HS=高自旋)变到W^(Ⅳ)—CN—Co^(Ⅲ)_(LS)(LS=低自旋),并伴随着宽度为27 K的热迟滞。Magnetic bistable materials featuring switchable spin states are of substantial interest in terms of their promising application in memory devices and switches.Here,we report a new magnetic bistable compound based on W^(Ⅴ)-Co^(Ⅱ)charge transfer.A 2D cyano-bridged heterobimetallic network{[W^(Ⅴ)(CN)_(8)]_(2)[Co^(Ⅱ)(4-nvp)_(4)]_(3)}·4CH_(3)OH(1)(4-nvp=4-(2-(naphthalene-1-yl)vinyl)pyridine)is synthesized by incorporating the 4-nvp into the cyano-bridged W^(Ⅴ)-Co^(Ⅱ)layer framework to provide intra-and intermolecularπ-πinteraction.Magnetic studies show that compound 1 exhibits a reversible electron-transfer-coupled spin transition(ETCST)with interconversion between the W^(Ⅴ)—CN—Co^(Ⅱ)_(HS)(HS=high spin)and W^(Ⅳ)—CN—Co^(Ⅲ)_(LS)(LS=low spin)linkages,accompanied by a thermal hysteresis with a width of about 27 K.CCDC:2216222,1(120 K);2215990,1(295 K).

关 键 词：电子转移耦合诱导自旋转变 氰基桥联 二维网络结构 Π-Π相互作用 

分 类 号：O614.613[理学—无机化学] O614.812[理学—化学]