氰根和酚氧桥联M(Ⅱ)-Mn(Ⅲ)(M=Ru和Os)二维配合物的合成、结构与磁性

摘要

Two new M(Ⅱ)-Mn(Ⅲ) complexes {[Mn(Ⅲ)(salen)]4[Mn(Ⅲ)(salen)(H2O)]2[M(Ⅱ)(CN)6]｝(ClO4)2· 2H2O (M=Ru (1) and Os (2)) (salen2-=N,N'-ethylenebis(salicylideneaminato)dianion) have been synthesized based on [Mn(Ⅲ)(salen)]+ segment and hexacyanide-containing building blocks [M(Ⅱ)(CN)6]4-.Single crystal X-ray diffraction analyses show that both complexes are isostructurally two-dimensional (2D) structures in which cyanide-bridged heptanuclear [Mn(Ⅲ)6M(Ⅱ)]2+ units are linked together by double phenolate bridges.Magnetic studies show that they are abnormal antiferromagnetic through the double phenolate bridges with the magnetic coupling constant J=-0.340 cm-1 for 1 and-0.561 cm-1 for 2 based on the spin exchange Hamiltonian (H)=-2jmNmN(S)Mn1(S)Mn2.CCDC:1447244,1;1447245,2.%基于六氰根构筑单元[M(Ⅱ)(CN)6]4-与[Mn(Ⅲ)(salen)]+模块反应合成了2个新型酚氧和氰根混合桥联的M(Ⅱ)-Mn(Ⅲ)配合物{[Mn(Ⅲ)(salen)]4[Mn㈣(salen)(H2O)]2[M(Ⅱ)(CN)6]}(ClO4)2· 2H2O(M=Ru (1),Os (2),salen2-=双水杨酰胺乙基负离子).单晶衍射结果表明:它们是结构类似的二维化合物,其中氰根桥联的七核[Mn(Ⅲ)6M(Ⅱ)]2+单元进一步通过双酚氧桥相互连接构成二维层状结构.磁性研究表明:2个化合物通过酚氧桥均呈现反常的反铁磁耦合,基于自旋哈密顿算符(H)=-2jmNmN(S)Mn1(S)Mn2拟合得到它们的磁耦合常数分别是J=-0.340 cm-1 (1)和-0.561 cm-1 (2).