| 两个基于MnⅢ席夫碱氰基桥联化合物的合成、结构和磁性 |
| Synthesis, Structure and Magnetic Properties of Two Cyano-Bridged Complexes Based on MnⅢ-Schiff Bases |
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| 摘要: 本文利用MnⅢ席夫碱配合物作为前驱体，与含有氰根桥联配体的构筑基块K3[CoⅢ(CN)6]或Na[N(CN)2]反应合成了2个新的化合物[MnⅢ6(Salen)6(H2O)6·CoⅢ(CN)6][CoⅢ(CN)6]·6H2O (1)和[MnⅢ(5-Br)Salen·N(CN)2]·H2O (2)，其中 Salen为二-邻苯甲醛乙二胺。利用红外光谱、元素分析和X-射线单晶衍射分析对其结构进行了表征并测试了其磁学性质。结构分析表明化合物1由1个七核阳离子簇[Mn6Co]3+和一个平衡阴离子[Co(CN)6]3-组成的离子对化合物。而化合物2则为由MnⅢ组成的一维中性链结构，[N(CN)2]-利用叠氮桥联方式和金属离子配位。磁性研究表明，化合物1中[Co(CN)6]3-几乎不传递磁耦合作用，所以是一个顺磁体，但MnⅢ自身的零场分裂导致低χMT在低温时随温度下降而减小，而2则表现出弱的链内反铁磁性耦合作用。对比化合物1和2的磁性得知共轭体系[N(CN)2]-比同样是五原子配体[Co(CN)6]3-传递较强磁耦合作用。 |
| 关键词: 氰基桥联 席夫碱 晶体结构 磁性 锰配合物 |
| 基金项目: |
| Abstract: Based on MnⅢ-Schiff bases and the building blocks of K3[CoⅢ(CN)6] and Na[N(CN)2], two new cyano-bridged assemblies, [MnⅢ6(Salen)6(H2O)6·CoⅢ(CN)6][CoⅢ(CN)6]·6H2O (1) and [MnⅢ(5-Br)Salen·N(CN)2]·H2O (2) [salen=N,N′-ethylenebis (salicylideneiminato) dianion] have been synthesized and characterized structurally through IR, elemental analyses and single crystal X-ray structure analysis. The magnetic measurement of complex 1 and 2 were also carried out. The structure analysis reveals that 1 is a ion-pair complex, which is composed of a heptanuclear cation [Mn6Co]3+ and a counteranions [Co(CN)6]3-. In contrast to 1, complex 2 is a 1D neutral chain constructed by MnⅢ, which is found that [N(CN)2]- bridges between metal ions by a same mode as end-to-end N3-. Magnetic investigation indicates the overall paramagnetic nature of complex 1 with the strong zero field splitting (ZFS) effect of MnⅢ. However, complex 2 exhibits the weak intrachain antiferromagnetic coupling mediated by [N(CN)2]-, which implies that the conjugated [N(CN)2]- mediates the stronger magnetic coupling interaction between MnⅢ ions than [Co(CN)6]3- although they both are the five-atom bridging ligands. CCDC: 847146, 1; 847147, 2. |
| Keywords: cyano-bridged Schiff base crystal structure magnetic property manganese complex |
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| 罗新泽,周红波.两个基于MnⅢ席夫碱氰基桥联化合物的合成、结构和磁性[J].无机化学学报,2012,28(6):1183-1189. |
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