南京大学雷建平团队报道了定制顺反异构金属共价有机框架用于配位构型依赖的电化学发光。相关研究成果于2024年7月2日发表在《美国化学会杂志》。

精确操纵物质内的配位构型可以调节靶材料的能带结构和催化性能。金属-共价有机骨架（MCOFs）是一种融合了金属-有机框架（MOFs）和共价有机框架（COFs）优点的晶体材料，可以将预定的配位环境整合到框架中，以增强催化效果。

该研究中，研究人员以双（甘氨酸）铜为氨基配体，通过动力学和热力学上有利的途径精细地合成了异构MCOF，分别产生顺式MCOF和反式MCOF产物，从而在框架中引入了顺式-反式异构配位场。此外，氨基酸和β-酮烯胺键的柔性衍生的扭曲骨架赋予了反式MCOF令人惊讶的水分散性。与顺式MCOF相比，通过Cu节点对K₂S₂O₈的催化，反式异构体在阴极电化学发光中表现出显著增强。态密度分析表明，反式MCOF的d带中心更接近费米能级，导致更稳定的吸附结合以促进催化。

该研究首次报道了通过一种简单的方法构建预先设计的配位构型MCOF，为基于氨基酸的MCOF材料的设计提供了指导。

附：英文原文

Title: Tailored Cis–Trans Isomeric Metal–Covalent Organic Frameworks for Coordination Configuration-Dependent Electrochemiluminescence

Author: Tianrui Liu, Qiantu Tao, Yufei Wang, Rengan Luo, Jing Ma, Jianping Lei

Issue&Volume: July 2, 2024

Abstract: Precise manipulation of the coordination configuration within substances can modulate the band structure and catalytic properties of the target material. Metal–covalent organic frameworks (MCOFs), a crystal material amalgamating the benefits of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs), can integrate a predetermined coordination environment into the frameworks for amplifying the catalytic effect. In this study, we delicately synthesize isomeric MCOFs using bis(glycinato)copper as the aminoligand via kinetically and thermodynamically favorable pathways to yield cis-MCOF and trans-MCOF products, respectively, thereby introducing a cis–trans isomeric coordination field into the framework. Moreover, the twisted skeleton derived from the flexibility of amino acid and β-ketoenamine linkages endows trans-MCOF with surprising water dispersibility. Compared to cis-MCOF, the trans isomerism displays a significant enhancement in cathodic electrochemiluminescence via the catalysis of Cu nodes toward K2S2O8. The density of states analysis shows that the d-band center of trans-MCOF is closer to the Fermi level, leading to more stable adsorption binding to promote the catalysis. This study is the first report on constructing predesign coordination configuration MCOFs via an easy-handling method, which gives the guidelines for the design of amino acid-based MCOF materials.

DOI: 10.1021/jacs.4c02015

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c02015