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首页> 外文期刊>Russian Chemical Bulletin >Structure, magnetic, and electrochemical properties of complexes of 3d-metals as redox-active units for assembling coordination polymers and porous coordination polymer on their basis
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Structure, magnetic, and electrochemical properties of complexes of 3d-metals as redox-active units for assembling coordination polymers and porous coordination polymer on their basis

机译：用作配位聚合物和多孔配位聚合物的氧化还原活性单元的3d金属配合物的结构，磁性和电化学性质

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Mononuclear complexes ML2 (M-II = Fe, Co, Cu, Zn) and porous coordination polymer [{Fe2NiO(Piv)(6)}{CoL2}(1.5)] (n) (LH is the Schiff base of pyridine-4-carboxylic acid hydrazide and pyridine-2-carbaldehyde, and Piv(-) is pivalate) were synthesized and characterized. The structures of the compounds were determined by X-ray diffraction analyses. Each ML2 molecule contains two 4-pyridine fragments capable of coordinating metal ions. Polymer [{Fe2NiO(Piv)(6)}{CoL2}(1.5)] (n) was formed by cross-linking of trinuclear units with the CoL2 bridge. The temperature dependences of the magnetic susceptibility of CoL2, FeL2, and [{Fe2NiO(Piv)(6)}{CoL2}(1.5)] (n) were studied. The magnetic properties of [{Fe2NiO(Piv)(6)}{CoL2}(1.5)] (n) were described as a superposition of the susceptibilites of the trinuclear and mononuclear units, and their interaction was taken into account in the framework of the molecular field model. The magnetic properties of CoL2 in the individual state and in the framework of [{Fe2NiO(Piv)(6)}{CoL2}(1.5)] (n) were interpreted using a model taking into account the spin-orbit coupling in the Co2+ ion and the splitting of its levels by crystal field. For FeL2, a model taking into account the zero-field splitting of the ground state of the Fe2+ ion was used. Several redox processes were found for ML2 in a solution and for [{Fe2NiO(Piv)(6)}{CoL2}(1.5)] (n) in a suspension by cyclic voltammetry. The CoL2 and FeL2 complexes can catalyze the electrochemical dehalogenation of freon CF2ClCFCl2 but exhibit no activity in the dehalogenation of CHCl3; ZnL2 did not show catalytic activity in the dehalogenation of both substrates.
机译：单核络合物ML2（M-II = Fe，Co，Cu，Zn）和多孔配位聚合物[{Fe2NiO（Piv）（6）} {CoL2}（1.5）]（n）（LH是吡啶4的席夫碱合成了2-羧酸酰肼和吡啶-2-甲醛，Piv（-）是新戊酸酯）。化合物的结构通过X射线衍射分析确定。每个ML2分子均包含两个能够配位金属离子的4-吡啶片段。聚合物[{Fe2NiO（Piv）（6）} {CoL2}（1.5）]（n）通过三核单元与CoL2桥的交联形成。研究了CoL2，FeL2和[{Fe2NiO（Piv）（6）} {CoL2}（1.5）]（n）的磁化率与温度的关系。 [{Fe2NiO（Piv）（6）} {CoL2}（1.5）]（n）的磁性能被描述为三核和单核单元的磁化石的叠加，并且在以下条件下考虑了它们的相互作用：分子场模型。使用考虑了Co2 +中自旋轨道耦合的模型来解释CoL2在单个状态和[{Fe2NiO（Piv）（6）} {CoL2}（1.5）]（n）框架中的磁性离子及其能级通过晶体场的分裂。对于FeL2，使用考虑了Fe2 +离子基态的零场分裂的模型。通过循环伏安法测定了悬浮液中的ML2和悬浮液中的[{Fe2NiO（Piv）（6）} {CoL2}（1.5）]（n）的几种氧化还原过程。 CoL2和FeL2配合物可以催化氟利昂CF2ClCFCl2的电化学脱卤，但在CHCl3的脱卤中没有活性。 ZnL2在两种底物的脱卤中均未显示催化活性。

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