Towards the Formation of Porous Architecture via Self-Assembly of Antiaromatic Dibenzopentalene: A Computational Study

Aromatic monomers are widely used as the backbone of porous materials such as Covalent Organic Frameworks (COFs) and Metal Organic Frameworks (MOFs), as their rigid and planar structures promote crystallinity and structural order in these frameworks. In addition, aromatic monomers themselves can self-assemble into porous architectures through noncovalent interactions; however, only a limited number of such examples have been reported. Here, we investigate the self-assembly of antiaromatic dibenzopentalene (DBP) to form a stable Antiaromatic Self-assembled Porous Framework (ASPF). Density Functional Theory (DFT) calculations reveal how substitution, substituent position, and annulation influence the stability of the pentalene (PN) core. Molecular dynamics (MD) simulations further ascertain that DBP, stabilized by benzene annulation, can spontaneously organize into a porous framework even in the absence of covalent or coordination bonds. This work aims to establish antiaromatic molecules as a new class of building blocks for porous materials with potential applications.