B31- and B32-: chiral quasi-planar boron clusters.

Abstract

Chirality plays an important role in nature. Nanoclusters can also exhibit chiral properties. We report herein a joint experimental and theoretical investigation on the geometric and electronic structures of B31- and B32- clusters, using photoelectron spectroscopy in combination with first-principles calculations. Two degenerate quasi-planar chiral C1 enantiomers (I and II, 1A) with a central hexagonal vacancy are identified as the global minima of B31-. For B32-, two degenerate boat-like quasi-planar chiral C2 structures (VI and VII, 2A) with a central hexagonal vacancy are also found as the global minima, with a low-lying chair-like Ci B32- (VIII, 2Au) also present in the experiment as a minor isomer. The chiral conversions in quasi-planar B31- and B32- clusters are investigated and relatively low barriers are found due to the high flexibility of these monolayer clusters, which feature multiple delocalized σ and π bonds over buckled molecular surfaces.