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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Copper(II) complexes of omega-hydroxy-functionalized N-salicylidenehydrazides show pH-controlled switching between dicationic dimers and neutral one-dimensional coordination polymers
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Copper(II) complexes of omega-hydroxy-functionalized N-salicylidenehydrazides show pH-controlled switching between dicationic dimers and neutral one-dimensional coordination polymers

机译:ω-羟基官能化的N-水杨酰肼的铜(II)配合物在二聚体和中性一维配位聚合物之间显示pH控制的转换

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摘要

New copper(II) complexes of the hydrazone ligands H(2)salhyhb, H(2)salhyhp, and H(2)salhyhh, derived from salicylaldehyde and omega-hydroxy carbonic acid hydrazides, have been synthesized and physically characterized. Two fundamental structures were found in solid state depending on the pH-value of the reaction solution. Acidic conditions lead to the formation of the di-mu-phenoxo-bridged dicationic complex dimers [{Cu(Hsalhyhb)}(2)](2+) (1a), [{Cu(Hsalhyhp)}(2)](2+) (2a), and [{Cu(Hsalhyhb)}(2)](2+) (3a), isolated as perchlorate salts. The dimeric complexes show strong antiferromagnetic coupling with J = -399 (1a), -410 (2a), and -311 cm(-1) (3a). Higher pH-values resulted in the aggregation of neutral copper ligand fragments to the one-dimensional coordination polymers [{Cu(salhyhb)}(n)] (1b), [{Cu(salhyhp)}(n)] (2b), and [{Cu(salhyhh)}(n)] (3b). 3b has been examined by means of X-ray crystallography and represents the first example of a structurally characterized neutral copper(II) N-salicylidenehydrazide complex without additional ligands. The magnetic interactions in the polymers are also antiferromagnetic with J = -125 (1b), -136 (2b), and -148 cm(-1) (3b), but strongly reduced compared to the corresponding dimeric complexes. The two basic structure types can be reversibly interconverted simply by pH-control.
机译:sal配体H(2)salhyhb,H(2)salhyhp和H(2)salhyhh的新铜(II)配合物已从水杨醛和ω-羟基碳酸酰肼衍生而来,并进行了物理表征。根据反应溶液的pH值,发现两个基本结构处于固态。酸性条件导致di-phen-oxoxo-bridged dicic复杂二聚体的形成[{Cu(Hsalhyhb)}(2)](2+)(1a),[{Cu(Hsalhyhp)}(2)](2 +)(2a)和[{Cu(Hsalhyhb)}(2)](2+)(3a)分离为高氯酸盐。二聚体配合物显示出强反铁磁耦合,其中J = -399(1a),-410(2a)和-311 cm(-1)(3a)。较高的pH值导致中性铜配体片段聚集到一维配位聚合物[{Cu(salhyhb)}(n)](1b),[{Cu(salhyhp)}(n)](2b),和[{Cu(salhyhh)}(n)](3b)。已经通过X射线晶体学检查了图3b,并且图3b代表结构特征化的中性铜(II)N-水杨亚水合肼配合物的第一个实例,其没有额外的配体。聚合物中的磁性相互作用也是反铁磁性的,J = -125(1b),-136(2b)和-148 cm(-1)(3b),但与相应的二聚体配合物相比大大降低。两种基本结构类型可以通过pH控制简单地可逆地相互转化。

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