Computational Insight Towards the Selective Chemisorption of Toxic Carbonmonoxide by an Antiaromatic COF

ABSTRACT Carbon monoxide () is one of the most prevalent and toxic atmospheric pollutants, known for its strong affinity toward hemoglobin, possessing serious health risks. Hence, the development of materials capable of capturing is of significant importance. Conventional porous materials such as metal–organic frameworks (MOFs), porous‐organic polymers (POPs), and zeolites have exhibited potential for adsorption. In contrast, covalent‐organic frameworks (COFs) have not been explored for capture due to their stable aromatic monomeric units, which limit chemisorption. Herein, we report a novel designed antiaromatic‐based COF incorporating a dibenzo[a,e]pentalene (DBP) monomer that enables efficient trapping via a chemisorption mechanism. Molecular dynamics (MD) simulations reveal that the DBP‐based building blocks can self‐assemble into a stable and porous COF framework. Furthermore, Density Functional Theory (DFT) calculations confirm that capture on the DBP moiety occurs via chemisorption, highlighting the crucial role of antiaromaticity in facilitating selective and stable adsorption within the COF structure for the first time.