含樟脑衍生物氰基桥联双金属配合物的合成、结构及磁性质(英文)

Synthesis,Crystal Structures,and Magnetic Properties of Two Cyano-bridged Heterobimetallic Complexes with Camphor Derivative Ligands

采用樟脑衍生物为配体,分别合成了氰基桥联Cu(Ⅱ)-Fe(Ⅲ)-Cu(Ⅱ)三核配合物[{Cu(D,L-La)2}2Fe(CN)6](ClO4)(1)和Mn"-Fe"双核配合物[Mn(D,L-Lb)(DMF)(Tp)Fe(CN)3·](H2O)6(2)。晶体结构分析表明,化合物1中Cu(Ⅱ)离子处于五配位的配位环境,分别和1个D-La,1个L-La及[Fe(CN)6]3-中的1个氰基配位,2个Cu(Ⅱ)离子通过[Fe(CN)6]3-桥联。通过分子间氢键作用,化合物1形成二维超分子网络结构。化合物2中,[(Tp)Fe(CN)3]-通过其中的1个氰基与[Mn(D,L-Lb)]+桥联,其中Mn(Ⅲ)离子为六配位,分别和四齿配体Lb的2个氧原子和2个氮原子、DMF的1个氧原子及[(Tp)Fe(CN)3]-中的氰基氮原子配位。磁性研究表明,在化合物1中,Cu(Ⅱ)离子与Fe(Ⅲ)离子之间表现出铁磁相互作用,用哈密顿函数■=-2J(1·2+2·3)对其χMT-T曲线进行拟合,得到1的朗日因子g为2.190,交换常数J为0.55cm-1。

A cyano-bridged trinuclear Cu ^Ⅱ2Fe^Ⅲ complex [{Cu（D,L-La）2}2Fe（CN）6]（ClO4） （1） （La= 1,2,2-trimethylcyclopentane-1,3-diamine） and a cyano-bridged binuclear Mn^Ⅲ-Fe^Ⅱ complex [Mn（D,L-Lb）（DMF）（Tp）Fe（CN）3]·（H2O）6 （2） （Lb=cis-N,N＇-（2-Hydroxybenzylidene）-1,2,2-trimethylcyclopenta-1,3-diamine） have been prepared and characterized. X-ray crystal structure analysis for complex 1 reveals that the copper ion is penta-coordinated by a D- and a L-diamine ligand, and two copper ions are bridge-connected by two cyanides from [Fe（CN）6]^3- in axial position. It shows a two-dimensional supramolecular network through hydrogen-bonding interaction. In complex 2, the manganese ion is six-coordinated by two oxygen atoms and two nitrogen atoms from a quadridentate ligand Lb, as well as one oxygen atom from DMF and one cyanide nitrogen atom from [（Tp）Fe（CN）3]^- in axial positions. Magnetic study shows intramolecular ferromagnetic interactions in complex 1. The best-fit for XMT vs T using the model H^ =-2J（S^1 ＋S^2＋S^2 -S^3）, leads to the parameters J=0.551 cm^-1 and g=2.190. CCDC： 626440, 1; 626439, 2.