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镍、铜和锌双核螺旋配合物:庞大基团如何影响其结构?

Nickel, copper, and zinc dinuclear helicates: how do bulky groups influence their architecture?

作者信息

Fernández-Fariña Sandra, Maneiro Marcelino, Zaragoza Guillermo, Seco José M, Pedrido Rosa, González-Noya Ana M

机构信息

Departamento de Química Inorgánica, Facultade de Ciencias, Campus Terra, Universidade de Santiago de Compostela, E-27002, Lugo, Spain.

Unidade de Difracción de Raios X, Edificio CACTUS, Universidade de Santiago de Compostela, Campus Sur, Santiago de Compostela, Galicia, E-15782, Spain.

出版信息

Dalton Trans. 2024 Mar 19;53(12):5676-5685. doi: 10.1039/d4dt00279b.

Abstract

The ligand design factors that may influence the isolation of metallosupramolecular helicates or mesocates still deserve to be investigated. In this sense, dinuclear nickel(II), copper(II) and zinc(II) compounds were obtained by electrochemical synthesis using a family of five Schiff base ligands, HL ( = 1-5), derived from bisphenylmethane and functionalized with bulky -butyl groups in the periphery and ethyl groups in the spacer. Six of the new complexes were characterized by X-ray crystallography, thus demonstrating that the helicate structure is predominant in the solid state. H NMR studies were performed for the zinc complexes to analyze if the helical architecture of the metal complexes is retained in solution. These studies reveal that the presence of a -butyl group in the position with respect to the OH group is an essential factor identified for the existence of a helicate conformation in solution.

摘要

可能影响金属超分子螺旋体或介观配合物分离的配体设计因素仍值得研究。从这个意义上讲,通过电化学合成,使用了一族五个席夫碱配体HL(= 1 - 5)获得了双核镍(II)、铜(II)和锌(II)化合物,这些配体由双苯甲烷衍生而来,在外围带有庞大的丁基,在间隔基中带有乙基。通过X射线晶体学对六种新配合物进行了表征,从而证明螺旋体结构在固态中占主导地位。对锌配合物进行了¹H NMR研究,以分析金属配合物的螺旋结构在溶液中是否得以保留。这些研究表明,相对于OH基团,在α位存在丁基是溶液中存在螺旋体构象所确定的一个关键因素。

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