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基于六配位硅中心的螺旋配合物的构建。

Construction of helicates based on six-coordinated silicon centres.

作者信息

Guan Yu-Tao, Ji Heng, Yang Ju, Yu Sai-Sai, Liu Ming

机构信息

Department of Chemistry, Zhejiang University Hangzhou 310058 China.

Hangzhou Global Scientific and Technological Innovation Center (HIC), Zhejiang University Xiaoshan Hangzhou 311215 China

出版信息

Chem Sci. 2025 Jul 16. doi: 10.1039/d5sc03271g.

Abstract

A class of triple-stranded helicates based on six-coordinate silicon centres has been constructed through self-assembly of achiral catechol ligands, as confirmed by single-crystal X-ray diffraction. These architectures demonstrate stability across physiological environments at pH = 3-12. Ligand rigidity dictates chiral configurations: rigid scaffolds form ΛΛ/ΔΔ racemic helicates, while flexible linkers enable dynamic equilibration with ΛΔ mesostates, observable by NMR. Host-guest interactions drive mesocate to helicate conversion, imparting cage-like guest recognition behavior. The helicates combine the biocompatibility of silicon with ligand-controlled chirality switching, offering potential for biomimetic applications.

摘要

通过非手性儿茶酚配体的自组装构建了一类基于六配位硅中心的三链螺旋体,单晶X射线衍射证实了这一点。这些结构在pH = 3-12的生理环境中表现出稳定性。配体刚性决定手性构型:刚性支架形成ΛΛ/ΔΔ外消旋螺旋体,而柔性连接体则能与ΛΔ介观态动态平衡,可通过核磁共振观察到。主客体相互作用驱动间苯二酚向螺旋体转化,赋予笼状客体识别行为。这些螺旋体将硅的生物相容性与配体控制的手性转换相结合,为仿生应用提供了潜力。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6a00/12376860/2cc456fdfb59/d5sc03271g-s1.jpg

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