Liu Zheng, Fang Jun-Jie, Wang Zhi-Yi, Xie Yun-Peng, Lu Xing
State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China.
School of Chemistry and Chemical Engineering, Hainan University, No. 58, Renmin Avenue, Haikou 570228, China.
Nanoscale. 2024 Oct 3;16(38):17817-17824. doi: 10.1039/d4nr02543a.
The utilization of bifunctional ligands, specifically pyridine carboxylic acids, endowed with dual coordination sites, has been instrumental in the assembly of polymer materials. The ambidentate characteristics of these ligands play a crucial role in shaping the structure and framework of cluster-based polymers. In this study, we have synthesized a diverse array of multidimensional copper(I) alkynyl cluster-based polymers (CACPs) by employing four distinct pyridine carboxylic acids - namely, isonicotinic acid (INA), 6-isoquinolinecarboxylic acid (IQL), 4-pyridin-4-yl-benzoic acid (4-PyBA), and 3-pyridin-4-yl-benzoic acid (3-PyBA) - as linking ligands. These pyridine carboxylic acids not only serve as protective ligands but also act as pivotal linkers in constructing the cluster-based framework materials, exerting significant influence on the overall framework structures. Furthermore, the incorporation of auxiliary ligands has been shown to markedly impact the structural integrity and framework architecture of the CACPs. This study elucidates the indispensable role of pyridine carboxylic acids in the construction and stabilization of cluster-based framework materials, thereby advancing the frontier of research in metal cluster-based framework material synthesis.
双功能配体，特别是具有双配位位点的吡啶羧酸，在聚合物材料的组装中发挥了重要作用。这些配体的两可特性在塑造基于簇的聚合物的结构和框架方面起着关键作用。在本研究中，我们通过使用四种不同的吡啶羧酸——即异烟酸（INA）、6-异喹啉羧酸（IQL）、4-吡啶-4-基苯甲酸（4-PyBA）和3-吡啶-4-基苯甲酸（3-PyBA）——作为连接配体，合成了多种多维基于铜（I）炔基簇的聚合物（CACP）。这些吡啶羧酸不仅作为保护配体，而且在构建基于簇的骨架材料中充当关键连接体，对整体骨架结构产生重大影响。此外，已证明引入辅助配体对CACP的结构完整性和骨架结构有显著影响。本研究阐明了吡啶羧酸在基于簇的骨架材料的构建和稳定中的不可或缺的作用，从而推动了基于金属簇的骨架材料合成研究的前沿。
