W-X-M transformations in isomerization of B39- borospherenes

The Stone-Wales transformation plays an important role in the isomerization of fullerenes and graphenic systems. The continuous conversions between neighboring six- and seven-membered rings in the borospherene (all-boron fullerene) B-40 had been discovered (Martinez-Guajardo et al. Sci. Rep. 5, 11287 (2015)). In the first axially chiral borospherenes C-3 B-39(-) and C-2 B-39(-), we identify three active boron atoms which are located at the center of three alternative sites involving five boron atoms denoted as W, X, and M, respectively. The concerted movements of these active boron atoms and their close neighbors between neighboring six- and seven-membered rings define the W-X-M transformation of borospherenes. Extensive first-principles molecular dynamics simulations and quadratic synchronous transit transition-state searches indicate that, via three transition states (TS1, TS2, and TS3) and two intermediate species (M1 and M2), the three-step W-X-M transformations convert the C-3 B-39(-) global minimum into its C-2 isomer at room temperature (300 K) and vice versa. The maximum barriers are only 3.89 kcal/mol from C-3 to C-2 B-39(-) and 2.1 kcal/mol from C-2 to C-3 B-39(-), rendering dynamic fluxionalities to these borospherenes. Therefore, the W-X-M transformation plays an important role in the borospherenes and borospherene-based nanostructures. (C) 2016 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).