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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Discrete trinuclear copper(II) compounds as building blocks: the influence of the peripheral substituents on the magnetic coupling in oxamato-bridged complexes
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Discrete trinuclear copper(II) compounds as building blocks: the influence of the peripheral substituents on the magnetic coupling in oxamato-bridged complexes

机译：离散的三核铜（II）化合物作为构建基块：外围取代基对恶唑桥复合物中磁耦合的影响

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摘要

Two new trinuclear copper(II) complexes without end-capping ligands, (Bu_4N)_2[Cu(dmso)_2{Cu(dnopba)-(dmso)}_2] (1) and (Bu_4N)_2[Cu(dmso)_2{Cu(dcopba)(dmso)}_2] (2) [dnopba = 4,5-dinitro-ortho-phenylenebis-(oxamate), dcopba = 4,5-dichloro-ortho-phenylenebis(oxamate), Bu_4N~+ = tetra-n-butylammonium and dmso = dimethylsulfoxide], were synthesized and their structures were determined by single crystal X-ray diffraction. The crystal structures of 1 and 2 consist of two outer bis(oxamato)(dmso)cuprate(II) units which act as bidentate ligands toward a trans-bis(dmso)copper(II) inner entity leading to centrosymmetric tricopper(II) complexes with copper–copper separations across the oxamate bridges of 5.1916(3) (1) and 5.1776(3) ? (2). The peripheral copper(II) ions in 1 and 2 are five-coordinate in somewhat distorted square pyramidal environments with a dmso molecule filling the apical position whereas the inner copper(II) ion is six-coordinate in an elongated octahedral environment with two dmso molecules in the axial sites. The investigation of their magnetic properties in the temperature range 2.0–300 K shows the occurrence of a strong intramolecular antiferromagnetic coupling between the copper(II) ions through the oxamate bridges [J_1 = ?296(1) (1) and ?334(1) cm~(?1) (2), the Hamiltonian being defined as ? = ?J_1(?_(Cu2)·?_(Cu1) + ?_(Cu2)·?_(Cu1)’)], which leads to a low-lying spin doublet at low temperatures. Density functional theory calculations (DFT) have been used to substantiate these magnetic couplings and also to analyse the influence exerted on these interactions by the type of substituent at the 4,5-positions from the phenylene ring of the bis(oxamate) ligand.
机译：两个没有封端配体的新三核铜（II）配合物（Bu_4N）_2 [Cu（dmso）_2 {Cu（dnopba）-（dmso）} _ 2]（1）和（Bu_4N）_2 [Cu（dmso）_2 {Cu（dcopba）（dmso）} _ 2]（2）[dnopba = 4,5-二硝基邻苯撑双（草酸酯），dcopba = 4,5-二氯邻苯撑双（草酸酯），Bu_4N〜+ =合成了四正丁基铵和dmso =二甲基亚砜]，并通过单晶X射线衍射确定了它们的结构。 1和2的晶体结构由两个外部双（oxamato）（dmso）cuprate（II）单元组成，它们作为反式双（dmso）copper（II）内部实体的双齿配体，导致中心对称的tricopper（II）络合物在5.1916（3）（1）和5.1776（3）的草酸盐桥上有铜-铜间隔？ （2）。 1和2中的外围铜（II）离子在有些扭曲的方形锥体环境中具有五坐标，其中dmso分子填充顶端位置，而内部铜（II）离子在细长的八面体环境中具有六坐标，其中有两个dmso分子在轴向部位。在2.0–300 K的温度范围内对它们的磁性进行了研究，结果表明，通过草酸盐桥，铜（II）离子之间存在强分子内反铁磁耦合[J_1 =？296（1）（1）和？334（1） ）cm〜（？1）（2），哈密顿量定义为？ =ΔJ_1（Δ_（Cu2）·Δ_（Cu1）+Δ_（Cu2）·Δ_（Cu1）’）]，这导致在低温下的低自旋双峰。密度泛函理论计算（DFT）已用于证实这些磁耦合，还用于分析双（草酸酯）配体的亚苯基环在4,5-位上的取代基类型对这些相互作用的影响。

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