In this study, the heterogeneously catalized alkoxycarbonylation of olefins with CO2 based on the SILP strategy was reported for the first time. The catalyst Ru@SILP was accessed by immobilization of...

In this study, the covalent bonding of linear poly­(ionic liquid)­s (PILs) with covalent organic frameworks (COFs) was accessed by copolymerization of a vinyl-decorated COF with 4-vinylbenzyl chloride, followed by quaternization with tertiary amines. The resultant PIL–COF composite by anchoring a proper content of vinyl sites on the COF-based comonomer retains the crystallinity and porosity, thereby facilitating access of the reactants to the catalytic active sites. As a proof of concept, the dehydrative transformation of sorbitol into isosorbide was selected as a benchmark reaction, whose rate improved significantly in the presence of PIL–COF-0.33 compared with those of individual components and the mesoporous PIL counterpart due to uniform pore sizes and flexible linear catalytic chains. In addition, the hybrids bearing a chemical cross-linkage between PILs and COFs are robust, and PIL–COF-0.33 can be recovered and reused for 10 runs without significant reactivity loss. These findings provide the basis for a novel design concept for achieving both efficient and stable IL catalysis.