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

Carbon monoxide ( C O ) 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 C O is of significant importance. Conventional porous materials such as metal-organic frameworks (MOFs), porous-organic polymers (POPs), and zeolites have exhibited potential for C O adsorption. In contrast, covalent-organic frameworks (COFs) have not been explored for C O 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 C O 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 C O capture on the DBP moiety occurs via chemisorption, highlighting the crucial role of antiaromaticity in facilitating selective and stable C O adsorption within the COF structure for the first time.