Three dinuclear cyanide-bridged complexes[Fe^(Ⅱ)(PY_(5)OMe_(2))CNM^(Ⅱ)(PY_(5)OMe_(2))](OTf)_(3) (M=Fe1,M=Co 2,M=Mn 3)(PY_(5)OMe_(2)=2,6-bis-((2-pyridyl)methoxymethane)pyridine OTf=CF_(3)SO_(3)^(-)) have been synthes...Three dinuclear cyanide-bridged complexes[Fe^(Ⅱ)(PY_(5)OMe_(2))CNM^(Ⅱ)(PY_(5)OMe_(2))](OTf)_(3) (M=Fe1,M=Co 2,M=Mn 3)(PY_(5)OMe_(2)=2,6-bis-((2-pyridyl)methoxymethane)pyridine OTf=CF_(3)SO_(3)^(-)) have been synthesized and characterized.Single-crystal diffraction analyses show these three dinuclear compounds are very similar in structure.The measured ν(CN) results for compounds 1~3 suggest that Mn^(2+) is electron-poorer than Fe^(2+) and Co^(2+).Meanwhile,the temperature dependence of magnetic susceptibilities of complexes 1~3 reveals that in these three complexes,all the cyanide-carbon coordinated Fe(Ⅱ) is low-spin,and Co(Ⅱ) for 2 and Mn(Ⅱ) for 3are both in a high-spin state through 2~400 K but the cyanide-nitrogen coordinated Fe(Ⅱ) for complex 1 exhibits spin crossover (SCO) behavior over 300 K and a hysteresis of 36 K in both cooling and heating modes.展开更多
基金the National Natural Science Foundation of China(21773243,21973095)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20010200)。
文摘Three dinuclear cyanide-bridged complexes[Fe^(Ⅱ)(PY_(5)OMe_(2))CNM^(Ⅱ)(PY_(5)OMe_(2))](OTf)_(3) (M=Fe1,M=Co 2,M=Mn 3)(PY_(5)OMe_(2)=2,6-bis-((2-pyridyl)methoxymethane)pyridine OTf=CF_(3)SO_(3)^(-)) have been synthesized and characterized.Single-crystal diffraction analyses show these three dinuclear compounds are very similar in structure.The measured ν(CN) results for compounds 1~3 suggest that Mn^(2+) is electron-poorer than Fe^(2+) and Co^(2+).Meanwhile,the temperature dependence of magnetic susceptibilities of complexes 1~3 reveals that in these three complexes,all the cyanide-carbon coordinated Fe(Ⅱ) is low-spin,and Co(Ⅱ) for 2 and Mn(Ⅱ) for 3are both in a high-spin state through 2~400 K but the cyanide-nitrogen coordinated Fe(Ⅱ) for complex 1 exhibits spin crossover (SCO) behavior over 300 K and a hysteresis of 36 K in both cooling and heating modes.