A Macrocycle-Based Supramolecular Strategy for Interchangeable Screwdriver-Like On-Demand Post-Functionalization of Covalent Organic Framework

Liancheng Hu; Yimin Cai; Xuwen Guo; Li Wang; Yongjie Jiang; Xiaowei Li; Ning Liu; Wen Feng; Lihua Yuan

doi:10.1002/anie.202510534

A Macrocycle-Based Supramolecular Strategy for Interchangeable Screwdriver-Like On-Demand Post-Functionalization of Covalent Organic Framework

Angew Chem Int Ed Engl. 2025 Jun 27:e202510534. doi: 10.1002/anie.202510534. Online ahead of print.

Authors

Liancheng Hu¹, Yimin Cai¹, Xuwen Guo¹, Li Wang¹, Yongjie Jiang², Xiaowei Li³, Ning Liu², Wen Feng², Lihua Yuan⁴

Affiliations

¹ Sichuan University - Wangjiang Campus: Sichuan University, Institute of Nuclear Science and Technology, Chengdu, CHINA.
² Sichuan University - Wangjiang Campus: Sichuan University, Institute of Nuclear Science and Technology, CHINA.
³ Sichuan University - Wangjiang Campus: Sichuan University, College of Chemistry, CHINA.
⁴ Sichuan University, College of Chemistry, 29 Wangjiang Road, 610064, Chengdu, CHINA.

PMID: 40574717
DOI: 10.1002/anie.202510534

Abstract

Constructing functionalized covalent organic frameworks (COFs) through post-functionalization constitutes one of the most important approaches to applications, but is frequently plagued by limited reaction types, tedious synthesis of different precursors, and time-consuming screening of synthetic parameters for COFs. Moreover, their functions are difficult to change once the functionalities are covalently attached to COF skeletons. Herein, we report a macrocycle-based supramolecular strategy for variable noncovalent post-functionalization on the same COF platform like an interchangeable screwdriver. As a proof of concept, pillar[5]arene (P5A) with electron-rich cavity is incorporated into COF as macrocycle host to anchor different electron-deficient guests of various functions. Such a design allows tunable post-functionalization of COF through host-guest interactions for customized utilities, which has been demonstrated by using a series of guests including organic salts for iodine capture and cyano-based ligands for metal ion separation. Removing the guests enables recycling of COF, consecutive reinstallation of different guests, and continuous use for implementing expected tasks. This work establishes a general noncovalent approach to on-demand interchangeable post-functionalization of COFs.

Keywords: covalent organic framework; host-guest systems; macrocycles; noncovalent interactions; supramolecular chemistry.