Guanidine-Based Covalent Organic Frameworks: Cooperation between Cores and Linkers for Chromic Sensing and Efficient CO<sub>2</sub> Conversion
Peng-Fei Mu, Lin Zhang, Ran Bu, Li-Fei Xiong, Yawei Liu, En‐Qing Gao
Abstract
C(sp)–H carboxylation with CO 2 is an attractive route of CO 2 utilization and is traditionally promoted by transition metal catalysts, and organocatalysis for the conversion remains rarely explored and challenging. In this article, triaminoguanidine-derived covalent organic frameworks (COFs) were used as platforms to develop heterogeneous organocatalysts for the reaction. We demonstrated that the COFs with guanidine cores and pyrazine linkers show high catalytic performance as a result of the cooperation between cores and linkers. The core is vitally important, which is deprotonated to the guanidinato group that binds and activates CO 2 . The pyrazine linker collaborates with the core to activate the C(sp)–H bond through hydrogen bonding. In addition, the COFs show acid- and base-responsive chromic behaviors thanks to the amphoteric nature of the core and the auxochromic effect of the pyrazine linker. The work opens up new avenues to organocatalysts for C–H carboxylation and chromic materials for sensing and switching applications.