Using a self-assembly process involving a[Mo^(Ⅲ)(CN)_(7)]^(4−)unit,an Fe^(Ⅱ) ion,and a 1,4-bis(4H-1,2,4-triazol-4-yl)benzene(btb)ligand,we have synthesized a novel coordination polymer,denoted as{K_(2)Fe^(Ⅱ)(btb)[M...Using a self-assembly process involving a[Mo^(Ⅲ)(CN)_(7)]^(4−)unit,an Fe^(Ⅱ) ion,and a 1,4-bis(4H-1,2,4-triazol-4-yl)benzene(btb)ligand,we have synthesized a novel coordination polymer,denoted as{K_(2)Fe^(Ⅱ)(btb)[Mo^(Ⅲ)(CN)_(7)]·5H_(2)O}n(1).Single-crystal structure analysis revealed a three-dimensional(3D)Hofmann-type framework for compound 1.The[Mo^(Ⅲ)(CN)_(7)]^(4−)unit engaged four cyanide groups to coordinate with Fe^(Ⅱ) ions,creating an anionic two-dimensional(2D)cyano-bridged layer of{Fe^(Ⅱ)[Mo^(Ⅲ)(CN)_(7)]}_(n).The btb ligands,in turn,coordinated axially with the Fe^(Ⅱ) ions,bridging adjacent 2D layers and thus constructing a 3D framework.Magnetic studies have shown that compound 1 exhibits a hysteretic one-step spin-crossover behavior.Moreover,a ferrimagnetic ordering with a critical temperature of approximately 65 K was also observed,which may be ascribed to the compound’s“core-shell”architecture:the main core is responsible for the SCO behavior,while the shell contributes to the ferrimagnetic characteristics.To the best of our knowledge,this is the first observation of spin-crossover behavior in compounds based on the[Mo^(Ⅲ)(CN)_(7)]^(4−)unit.展开更多
基金supported by the National Natural Science Foundation of China(22273036 and 21973039)。
文摘Using a self-assembly process involving a[Mo^(Ⅲ)(CN)_(7)]^(4−)unit,an Fe^(Ⅱ) ion,and a 1,4-bis(4H-1,2,4-triazol-4-yl)benzene(btb)ligand,we have synthesized a novel coordination polymer,denoted as{K_(2)Fe^(Ⅱ)(btb)[Mo^(Ⅲ)(CN)_(7)]·5H_(2)O}n(1).Single-crystal structure analysis revealed a three-dimensional(3D)Hofmann-type framework for compound 1.The[Mo^(Ⅲ)(CN)_(7)]^(4−)unit engaged four cyanide groups to coordinate with Fe^(Ⅱ) ions,creating an anionic two-dimensional(2D)cyano-bridged layer of{Fe^(Ⅱ)[Mo^(Ⅲ)(CN)_(7)]}_(n).The btb ligands,in turn,coordinated axially with the Fe^(Ⅱ) ions,bridging adjacent 2D layers and thus constructing a 3D framework.Magnetic studies have shown that compound 1 exhibits a hysteretic one-step spin-crossover behavior.Moreover,a ferrimagnetic ordering with a critical temperature of approximately 65 K was also observed,which may be ascribed to the compound’s“core-shell”architecture:the main core is responsible for the SCO behavior,while the shell contributes to the ferrimagnetic characteristics.To the best of our knowledge,this is the first observation of spin-crossover behavior in compounds based on the[Mo^(Ⅲ)(CN)_(7)]^(4−)unit.
