暨南大学化学与材料科学学院Xiao-Ping Zhou研究组在金属有机化学研究中取得进展。他们的最新研究提出了异金属有机胶囊的精确合成后修饰用于选择性包封四面体阴离子。该研究于2024年2月21日发表于国际一流学术期刊《德国应用化学》杂志上。

在该研究中课题组报道了一种含有Pd(II)和CuL1金属配体的管状异金属Pd₃Cu₆L1₆胶囊的自组装。该胶囊经过两个三齿阴离子配体(L2)的进一步修饰，得到具有Edshammer多面体结构的双聚Pd₃Cu₆L1₆L2₂胶囊。通过使用过渡金属离子、酸和氧化剂，二头包覆的胶囊可转换为未包覆的胶囊。这种不封顶的形式可以在加入溴离子和碱后恢复为封顶结构。

有趣的是，引入Ag⁺导致一个L2配体从二头包膜中去除，产生单帽Pd₃Cu₆L1₆L2结构。此外，阴离子的大小对胶囊合成后修饰的精确控制具有重要影响。实验证明，这些胶囊选择性地封装了四面体阴离子，为智能分子递送系统的设计提供了一种新的方法。

据介绍，合成后改性对于精确调整先进材料的结构和功能起着至关重要的作用。

附：英文原文

Title: Precise Post-Synthetic Modification of Heterometal-Organic Capsules for Selectively Encapsulating Tetrahedral Anions

Author: Ya-Liang Lai, Mo Xie, Xian-Chao Zhou, Xue-Zhi Wang, Xiao-Wei Zhu, Dong Luo, Xiao-Ping Zhou, Dan Li

Issue&Volume: 2024-02-21

Abstract: Post-synthetic modification plays a crucial role in precisely adjusting the structure and functions of advanced materials. Herein, we report the self-assembly of a tubular heterometallic Pd3Cu6L16 capsule, incorporating Pd(II) and CuL1 metalloligands. This capsule undergoes further modification with two tridentate anionic ligands (L2) resulting in a bicapped Pd3Cu6L16L22 capsule with an Edshammer polyhedral structure. By employing transition metal ions, acid, and oxidation agents, the bicapped capsule is convertible to an uncapped one. This uncapped form can then revert to the bicapped structure with the addition of Br- ions and a base. Interestingly, introducing Ag+ leads to the removal of one L2 ligand from the bicapped capsule, yielding a mono-capped Pd3Cu6L16L2 structure. Furthermore, the size of anions critically influences the precisely controlling the post-synthetic modifications of the capsules. It was demonstrated that these capsules selectively encapsulate the tetrahedral anions, offering a novel approach in the design of intelligent molecular delivery systems.

DOI: 10.1002/anie.202402829

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202402829