Coordination-driven design principles for boron fullerenes and borophenes: a predictive framework linking theory and experiment

Abstract A comprehensive first-principles analysis of boron fullerenes and two-dimensional boron sheets is presented, unified by a coordination-based classification with direct experimental relevance. Analysis of over a dozen boron nanostructures, including the experimentally realized B ₄₀ and B ₈₀ cages and multiple borophenes, reveals systematic trends in stability, electronic structure, and magnetism as functions of local atomic coordination (4-, 5-, and 6-fold). A size-dependent energetic scaling relation captures the convergence of fullerene cohesive energies toward those of 2D boron sheets, with the fitted exponent distinguishing two structural families. Direct structural correspondences between finite cages and experimentally synthesized borophenes are identified: B {}₄₀↔{χ}₃ , B {}₆₅↔{β}₁₂ , B {}₈₀↔α , and B {}₉₂↔bt . These links provide a predictive route for designing boron-based nanostructures with targeted properties. Predicted properties include large HOMO–LUMO gaps in B ₆₅ (1.06 eV) and B ₉₂ (2.16 eV) and a magnetic moment of B ₆₅ of 3{μ}_B . By connecting zero- and two-dimensional boron architectures through a chemically meaningful coordination descriptor, the framework offers experimentally actionable guidance for the synthesis and design of boron nanomaterials.