Wang Yao, Chang Jin-Ping, Xu Rui, Bai Sha, Wang Dong, Yang Guo-Ping, Sun Li-Ying, Li Peng, Han Ying-Feng
Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438, P. R. China.
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, College of Chemistry and Materials Science, Northwest University, Xi'an 710127, P. R. China.
Chem Soc Rev. 2021 Dec 13;50(24):13559-13586. doi: 10.1039/d1cs00296a.
Though N-heterocyclic carbenes (NHCs) have emerged as diverse and powerful discrete functional molecules in pharmaceutics, nanotechnology, and catalysis over decades, the heterogenization of NHCs and their precursors for broader applications in porous materials, like metal-organic frameworks (MOFs), porous coordination polymers (PCPs), covalent-organic frameworks (COFs), porous organic polymers (POPs), and porous organometallic cages (POMCs) was not extensively studied until the last ten years. By or post-synthetic modification (PSM) methods, myriads of NHCs and their precursors containing building blocks were designed and integrated into MOFs, PCPs, COFs, POPs and POMCs to form various structures and porosities. Functionalisation with NHCs and their precursors significantly expands the scope of the potential applications of porous materials by tuning the pore surface chemical/physical properties, providing active sites for binding guest molecules and substrates and realizing recyclability. In this review, we summarise and discuss the recent progress on the synthetic methods, structural features, and promising applications of NHCs and their precursors in functionalised porous materials. At the end, a brief perspective on the encouraging future prospects and challenges in this contemporary field is presented. This review will serve as a guide for researchers to design and synthesize more novel porous materials functionalised with NHCs and their precursors.
尽管几十年来,N-杂环卡宾(NHCs)已成为制药、纳米技术和催化领域中多样且强大的离散功能分子,但直到最近十年,NHCs及其前体在多孔材料(如金属有机框架(MOFs)、多孔配位聚合物(PCPs)、共价有机框架(COFs)、多孔有机聚合物(POPs)和多孔有机金属笼(POMCs))中的异质化研究才得到广泛开展。通过原位或后合成修饰(PSM)方法,设计并将无数含有结构单元的NHCs及其前体整合到MOFs、PCPs、COFs、POPs和POMCs中,以形成各种结构和孔隙率。用NHCs及其前体进行功能化,通过调节孔表面的化学/物理性质,为结合客体分子和底物提供活性位点并实现可回收性,显著扩大了多孔材料潜在应用的范围。在本综述中,我们总结并讨论了NHCs及其前体在功能化多孔材料中的合成方法、结构特征和有前景的应用方面的最新进展。最后,对这一当代领域令人鼓舞的未来前景和挑战给出了简要展望。本综述将为研究人员设计和合成更多用NHCs及其前体功能化的新型多孔材料提供指导。