中南大学Pingshan Wang研究组用预先设计的金属配体设计合成了分子风车。 相关论文发表在2020年11月18日出版的《美国化学会志》上。

课题组描述了通过三个理性预组装的金属配体L1-L3自组装的一系列风车形星状超分子。通过与含金属配合物的8倍Suzuki偶联反应，课题组合成的关键八价未络合的三吡啶金属配体L3，具有四种不同的三吡啶及三个<tpy-Ru²⁺-tpy>单元，这是迄今为止具有最多子单元的预组织模块。

根据几何互补原理和高“配位位点密度”，将这些金属配体与Zn²⁺离子进行组合，形成了风车形三角星P1、五角星P2和六角星P3，具有接近定量产率的精确控制的形状。分子量在16756 ~ 56053 Da之间，直径在6.7 ~ 13.6 nm之间，这些风车状结构的结构组成、形状和刚度已通过一维和二位核磁共振、电喷雾质谱、行波离子迁移率质谱、透射电子显微镜等手段进行了充分的表征。

据悉，开发一种方法来建立目标结构是合成化学的主要主题之一。然而，以可预测的方式实现多层精细的分子结构是非常具有挑战性的。

附：英文原文

Title: Construction of Macromolecular Pinwheels Using Predesigned Metalloligands

Author: Jun Wang, He Zhao, Mingzhao Chen, Zhiyuan Jiang, Feng Wang, Guotao Wang, Kaixiu Li, Zhe Zhang, Die Liu, Zhilong Jiang, Pingshan Wang

Issue&Volume: November 18, 2020

Abstract: Developing a methodology to build target structures is one of the major themes of synthetic chemistry. However, it has proven to be immensely challenging to achieve multilevel elaborate molecular architectures in a predictable way. Herein, we describe the self-assembly of a series of pinwheel-shaped starlike supramolecules through three rationally preorganized metalloligands L1–L3. The key octa-uncomplexed terpyridine (tpy) metalloligand L3, synthesized with an 8-fold Suzuki coupling reaction to metal-containing complexes, has four different types of terpyridines connected with three <tpy-Ru²⁺-tpy> units, making this the most subunits known so far for a preorganized module. Based on the principle of geometric complementation and the high “density of coordination sites”, these metalloligands were assembled with Zn2+ ions to form a pinwheel-shaped star trigon P1, pentagram P2, and hexagram P3 with precisely controlled shapes in nearly quantitative yields. With molecular weights ranging from 16756 to 56053 Da and diameters of 6.7–13.6 nm, the structural composition, shape, and rigidity of these pinwheel-shaped architectures have been fully characterized by 1D and 2D (NMR), electrospray ionization mass spectrometry, traveling-wave ion mobility mass spectrometry, and transmission electron microscopy.

DOI: 10.1021/jacs.0c08020

Source: https://pubs.acs.org/doi/10.1021/jacs.0c08020