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用于路易斯酸催化的邻苯二酚功能化缺陷共价有机框架的金属化

Metalation of Catechol-Functionalized Defective Covalent Organic Frameworks for Lewis Acid Catalysis.

作者信息

Shi Yanan, Zhang Xiaofei, Liu Haitao, Han Jianyu, Yang Zhongjie, Gu Lin, Tang Zhiyong

机构信息

CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, 100190, China.

Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, China.

出版信息

Small. 2020 Jun;16(24):e2001998. doi: 10.1002/smll.202001998. Epub 2020 May 17.

Abstract

Covalent organic frameworks (COFs) have emerged as a fascinating crystalline porous material and are widely used in the field of catalysis. However, developing simple approaches to fabricate conjugated COFs with specific functional groups remains a significant challenge. In this study, the construction of defective COF-LZU1 with Lewis acid sites embedded into the frameworks is fulfilled by a facile solvent-assisted ligand exchange method. A monodentate ligand, protocatechualdehyde, is successfully introduced into the skeleton of COF-LZU1, which endows the defects in the structure of COF-LZU1 via replacement of the original coordinated benzene-1,3,5-tricarbaldehyde ligand. As-synthesized defective COF-LZU1 decorated with protocatechualdehyde is rich of free hydroxy groups for chelating with active metal ions. Specifically, after combining with Fe , the defective COF-LZU1 shows excellent activity in catalytic alcoholysis of epoxides under mild conditions. The method reported here will open up the opportunity to incorporate different functional groups into COFs and enrich the strategies for creating new types of porous catalysts.

摘要

共价有机框架(COFs)已成为一种引人入胜的晶体多孔材料,并广泛应用于催化领域。然而,开发简单的方法来制备具有特定官能团的共轭COFs仍然是一项重大挑战。在本研究中,通过一种简便的溶剂辅助配体交换方法实现了将具有路易斯酸位点的缺陷型COF-LZU1构建到框架中。一种单齿配体,原儿茶醛,成功引入到COF-LZU1的骨架中,通过取代原来配位的苯-1,3,5-三甲醛配体,赋予了COF-LZU1结构中的缺陷。合成的用原儿茶醛修饰的缺陷型COF-LZU1富含用于与活性金属离子螯合的游离羟基。具体而言,与Fe结合后,缺陷型COF-LZU1在温和条件下对环氧化物的催化醇解表现出优异的活性。本文报道的方法将为将不同官能团引入COFs开辟机会,并丰富创建新型多孔催化剂的策略。

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