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源自6-取代-2-甲酰基苯酚的席夫碱配体的双核、四核和六核铁(III)、锰(II/III)和铜(II)配合物

Di-, tetra- and hexanuclear iron(III), manganese(II/III) and copper(II) complexes of Schiff-base ligands derived from 6-substituted-2-formylphenols.

作者信息

Lan Yanhua, Novitchi Ghenadie, Clérac Rodolphe, Tang Jin-Kui, Madhu N T, Hewitt Ian J, Anson Christopher E, Brooker Sally, Powell Annie K

机构信息

Institut für Anorganische Chemie der Universität Karlsruhe, Engesserstrasse Geb. 30.45, D-76128, Karlsruhe, Germany.

出版信息

Dalton Trans. 2009 Mar 14(10):1721-7. doi: 10.1039/b818113f. Epub 2009 Jan 19.

Abstract

Acyclic Schiff base ligands, derived from the condensation of 2,3-disubstituted benzaldehydes and 1,3-diaminopropan-2-ol, react with iron(II/III), manganese(II/III) and copper(II) salts to give di-, tetra- and hexanuclear complexes [Fe(III)(2)(L5)(2)].2MeOH (), [Fe(III)(4)(mu(3)-OMe)(2)(HL4)(2)Cl(2)] (), [Mn(II)(2)Mn(III)(2)(micro-OMe)(2)(HL4)(2)(DMF)(2)].2DMF () and [Cu(II)(6)(L5)(2)(micro(5)-SO(4))(2)(micro-SO(4))(MeOH)(2)].H(2)O.15.5(MeOH).15.5(MeCN) (). All compounds have been characterised by X-ray crystallography. Variable-temperature solid-state dc magnetisation studies have been performed in the temperature range 1.8-300 K. Antiferromagnetic interactions are present in all the compounds. The dinuclear compound has a zero total spin ground state with J = -9.66(1) cm(-1) and g = 2.07(1). The magnetic data for the tetranuclear compounds and have been interpreted using a tetranuclear butterfly model (b = body, w = wingtip) with the parameters: J(wb) = -9.35(4) cm(-1), J(bb) = -6.02(7) cm(-1), zJ' = -0.21(4) cm(-1) and g = 2.03(1) for ; and J(wb) = -3.40(3) cm(-1), J(bb) = -8.11(7) cm(-1), zJ' = -0.042(2) cm(-1) and g = 2.0 (fixed) for . The hexanuclear compound contains two {Cu(3)(L5)(MeOH)} units linked by three sulfate ligands: antiferromagnetic interactions are present in each trinuclear unit leading to two S = 1/2 motifs which do not or only very weakly interact across the sulfate bridges.

摘要

由2,3 - 二取代苯甲醛与1,3 - 二氨基丙 - 2 - 醇缩合得到的无环席夫碱配体,与铁(II/III)、锰(II/III)和铜(II)盐反应,生成二核、四核和六核配合物[Fe(III)(2)(L5)(2)].2MeOH ()、[Fe(III)(4)(μ(3)-OMe)(2)(HL4)(2)Cl(2)] ()、[Mn(II)(2)Mn(III)(2)(μ-OMe)(2)(HL4)(2)(DMF)(2)].2DMF ()和[Cu(II)(6)(L5)(2)(μ(5)-SO(4))(2)(μ-SO(4))(MeOH)(2)].H(2)O.15.5(MeOH).15.5(MeCN) ()。所有化合物均通过X射线晶体学进行了表征。在1.8 - 300 K的温度范围内进行了变温固态直流磁化研究。所有化合物中均存在反铁磁相互作用。二核化合物具有零总自旋基态,J = -9.66(1) cm(-1),g = 2.07(1)。四核化合物的磁数据已使用四核蝴蝶模型(b = 主体,w = 翼尖)进行解释,参数如下:对于 ,J(wb) = -9.35(4) cm(-1),J(bb) = -6.02(7) cm(-1),zJ' = -0.21(4) cm(-1),g = 2.03(1);对于 ,J(wb) = -3.40(3) cm(-1),J(bb) = -8.11(7) cm(-1),zJ' = -0.042(2) cm(-1),g = 2.0(固定)。六核化合物包含由三个硫酸根配体连接的两个{Cu(3)(L5)(MeOH)}单元:每个三核单元中存在反铁磁相互作用,导致两个S = 1/2基序,它们在硫酸根桥之间不相互作用或仅非常微弱地相互作用。

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