Despite their early experimental production and observation, the unambiguous molecular structures of metal-containing boron nitride (BN) nanocages still remain mysterious. It has been commonly assumed that this family of compounds has the metal atom confined inside the cage, just like their isoelectronic cousins, carbon metallofullerenes do. Here, we demonstrate that Ti(BN)n (nn = 12–24) complexes have, unexpectedly, an exohedral structure instead of an endohedral one, which could be verified by collision-induced dissociation experiments. The predicted global minimum structures exhibit some common bonding features accounting for their high stability, and could be readily synthesized under typical conditions for generating BN nanoclusters. The Ti doping dramatically changes not only the cage topology, but the arrangement of B and N atoms, endowing the resultant compounds with potential for CO2CO2 capture and nitrogen fixation. These findings may expand or alter the understanding of BN nanostructures functionalized with other transition metals.
Li Ruyi, a student for a Master’s degree at the College of Chemistry and Chemical Engineering of Yangzhou University is the first author of the paper. Wang Yang, currently working as Professor at the College of Chemistry and Chemical Engineering of Yangzhou University, is the corresponding author of the paper. (Nat. Commun., 2019, 10, 4908)
Read more: https://doi.org/10.1038/s41467-019-12877-0