Abstract

This work introduces a new family of hollow boron nitride (BN) nanostructures, designed as isoelectronic analogs to the carbon-based Gaudiene architectures reported by Sundholm and co-workers. The B36N36, B108N108, B216N216and B324N324cages were constructed by replacing C–C bonds in their carbon counterparts with B–N pairs. GFN2-xTB calculations, validated by DFT for B36N36, confirm all structures as stable minima with large HOMO–LUMO gaps. Chemical bonding analysis reveals electron localization around nitrogen atoms and a non-aromatic character. Tight-binding molecular dynamics simulations demonstrate exceptional thermal stability up to 1000 K, with all systems retaining their hollow topology; the B216N216cage exhibits superior resilience. At high temperatures, larger systems undergo a size-dependent transformation toward stable hexagonal BN motifs, accompanied by significant energy stabilization. These results establish a novel class of BN nanostructures with promising properties for nanotechnology applications. © 2025 Published by Elsevier B.V.