High-Symmetry Cage-like Molecule N20(C2B2)30: Computational Insight into Its Bonding and Reactivity

Abstract

On the basis of density functional theory (DFT) calculations and AIMD simulations, a novel Ih-symmetry cage-like molecule N20(C2B2)30 is constructed and characterized computationally. It is found that N20(C2B2)30 is structurally similar to fullerene C20, but it has high thermodynamic and kinetic stability. The designed N20(C2B2)30 exhibits strong chemical reactivities, including the Diels-Alder reaction with butadiene (C4H6) and cyclopentadiene (C5H6), as well as the [3+2] addition reaction with diazomethane (N2CH2). In addition, the presence of the boron site and the inverted C=C bond with the charge-shift (CS) bonding in N20(C2B2)30 makes it quite active not only for cycloaddition reaction but also for capture of small molecules (e.g. H2, CO, NO, and NO2). Once N20(C2B2)30 complexes with a transition metal (TM) ion, the resultant complexes (TM)N20(C2B2)30+ (TM=Cu, Ag, and Au) can bind inactive CO2 and N2O at the TM site. Furthermore, AuN20(C2B2)30+ is able to effectively separate CO2 and N2O. Owing to its unique porous structure and reactivity as well as the high stability, N20(C2B2)30 may further enrich the diversity of highly symmetrical molecular family.