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桥连阴离子对酚盐桥连的二吡啶甲胺锌配位络合物的结构和稳定性的影响

Effect of Bridging Anions on the Structure and Stability of Phenoxide Bridged Zinc Dipicolylamine Coordination Complexes.

作者信息

O'Neil Edward J, Jiang Hua, Smith Bradley D

机构信息

Department of Chemistry and Biochemistry, University of Notre Dame, 2365 Nieuwland Science Hall, Notre Dame, IN 46556.

出版信息

Supramol Chem. 2013 Jun 1;25(6):315-322. doi: 10.1080/10610278.2013.776170.

Abstract

A series of four related phenol derivatives, with 2,2'-dipicolylamine substituents at the ortho positions, were prepared and their Zn coordination complexes studied by spectroscopic methods. X-ray crystal diffraction analysis of a dinuclear zinc complex with two bridging acetate anions showed a ternary structure with highly charged interior and lipophilic exterior, which helps explain why this class of water-soluble complexes can effectively diffuse through cell membranes. The stability of the dinuclear zinc complexes in aqueous solution was found to be strongly anion dependent; that is, bridging oxyanions, such as acetate and pyrophosphate, lock the two Zn cations to the surrounding ligand and greatly enhance ligand/zinc affinity. Overall, the results provide new insight into the structural and mechanistic factors that control the recognition and chemosensing performance of phenoxide bridged dipicolylamine molecular probes.

摘要

制备了一系列在邻位带有2,2'-二甲基吡啶胺取代基的四个相关苯酚衍生物,并通过光谱方法研究了它们的锌配位络合物。对具有两个桥连醋酸根阴离子的双核锌络合物进行的X射线晶体衍射分析表明,其具有带高电荷的内部和亲脂性外部的三元结构,这有助于解释为何这类水溶性络合物能有效扩散穿过细胞膜。发现双核锌络合物在水溶液中的稳定性强烈依赖于阴离子;也就是说,桥连的氧阴离子,如醋酸根和焦磷酸根,将两个锌阳离子锁定在周围的配体上,并大大增强了配体/锌的亲和力。总体而言,这些结果为控制酚盐桥连二甲基吡啶胺分子探针的识别和化学传感性能的结构和机制因素提供了新的见解。

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