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螯合席夫碱辅助叠氮桥联 Mn(II)、Ni(II)和 Cu(II)磁性配位聚合物。

Chelating Schiff base assisted azide-bridged Mn(II), Ni(II) and Cu(II) magnetic coordination polymers.

机构信息

Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 3 Research Link, Singapore 117602, Singapore.

出版信息

Dalton Trans. 2012 Nov 21;41(43):13379-87. doi: 10.1039/c2dt31186k.

Abstract

Four new Mn(II), Ni(II) and Cu(II) coordination polymers [Mn2(L1)(μ(1,1)-N3)2(μ(1,3)-N3)2]n (1), [Ni(L2)2(μ(1,3)-N3)]n(ClO4)n (2), [Cu(L3)(μ(1,1)-N3)(N3)]n (3) and [Cu(L4)(μ(1,1)-N3)2]n (4) (L1 = N,N′-bis(2-pyridylmethylene)ethane-1,2-diamine, L2 = N-(2-pyridylmethylene)methylamine, L3 = N-(2-pyridylmethylene)-3-pyridylamine, L4 = N-(2-pyridylmethylene)-tbutylamine) have been synthesized and characterized by single-crystal X-ray analysis and magnetic measurements. Complex 1 indicates a stoichiometry-dependent structural change (based on Mn:L1:N3 = 2:1:4 molar ratio) and consists of two-dimensional (2-D) (4,4) net layers, in which Mn(II) centers are co-bridged by single end-to-end (EE), double end-on (EO) azide and chelate-bridging L1 ligands. Complex 2 shows a single EE azide-bridged one-dimensional (1-D) Ni(II) chain. Complexes 3 and 4 indicate single EO and double EO azide-bridged 1-D Cu(II) chains, respectively. Complex 1 exhibits weak ferromagnetism due to its intra-layer spin-canting with T(c) = 20 K. Complex 2 shows an unusual intra-chain ferromagnetic coupling and spin-canting behaviour. Both complexes 3 and 4 exhibit intra-chain antiferromagnetic interactions. Magneto-structural parameters for these related complexes were also discussed.

摘要

四种新的 Mn(II)、Ni(II) 和 Cu(II) 配位聚合物 [Mn2(L1)(μ(1,1)-N3)2(μ(1,3)-N3)2]n (1)、[Ni(L2)2(μ(1,3)-N3)]n(ClO4)n (2)、[Cu(L3)(μ(1,1)-N3)(N3)]n (3) 和 [Cu(L4)(μ(1,1)-N3)2]n (4) (L1 = N,N′-双(2-吡啶基亚甲基)乙二胺,L2 = N-(2-吡啶基亚甲基)甲胺,L3 = N-(2-吡啶基亚甲基)-3-吡啶胺,L4 = N-(2-吡啶基亚甲基)-叔丁胺)已通过单晶 X 射线分析和磁性测量进行了合成和表征。配合物 1 表明结构变化依赖于化学计量比(基于 Mn:L1:N3 = 2:1:4 的摩尔比),由二维(2-D)(4,4)网层组成,其中 Mn(II)中心由单端到端(EE)、双端到端(EO)叠氮和螯合桥联 L1 配体桥接。配合物 2 显示出一维(1-D)镍(II)链中单 EE 叠氮桥。配合物 3 和 4 分别表示单 EO 和双 EO 叠氮桥接的 1-D Cu(II)链。配合物 1 由于其层内自旋倾斜而表现出弱铁磁性质,T(c) = 20 K。配合物 2 表现出异常的链内铁磁耦合和自旋倾斜行为。配合物 3 和 4 均表现出链内反铁磁相互作用。还讨论了这些相关配合物的磁结构参数。

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