A Versatile Method for Functionalization of Covalent Organic Frameworks via Suzuki–Miyaura Cross‐Coupling

Post‐synthetic modification (PSM) is a prevalent and powerful strategy to introduce desired functionalities into covalent organic frameworks (COFs) for functional products, expediting their applications vastly. Herein, we demonstrate a PSM strategy for functionalizing brominated COFs via the well‐developed Suzuki–Miyaura cross‐coupling. By this, a variety of functionalities were installed into COFs efficiently, while the crystallinity and porosity of COFs was well‐retained. As a proof‐of‐concept, BrCOF‐2 was modified with trifluoromethyl groups to produce a SF6 adsorbent with remarkably enhanced properties. This facile and versatile approach opens a new door for the synthesis of functional COFs, and greatly expands the scope of their structural design aiming for various properties and applications. A versatile and efficient post‐synthetic modification (PSM) method for functionalizing COFs via Suzuki–Miyaura cross‐coupling is developed. Various functionalities were installed on the pore walls of brominated COFs, producing functional COFs. The trifluoromethyl functionalization endows the COF with significantly enhanced properties for SF6 adsorption and separation.