title: Planar dicyclic B6S6, B6S6(-), and B6S6(2-) clusters: boron sulfide analogues of naphthalene.
abstract: Inorganic analogues of hydrocarbons or polycyclic aromatic hydrocarbons (PAHs) are of current interest in chemistry. Based upon global structural searches and B3LYP and CCSD(T) calculations, we present herein the perfectly planar dicyclic boron sulfide clusters: D2h B6S6 (1, (1)Ag), D2h B6S6(-) (2, (2)B3u), and D2h B6S6(2-) (3, (1)Ag). These are the global minima of the systems, being at least 0.73, 0.81, and 0.53 eV lower in energy, respectively, than their alternative isomers at the CCSD(T) level. The D2h structures feature twin B3S2 five-membered rings, which are fused together via a B2 unit and terminated by two BS groups. Bonding analyses show that the closed-shell B6S6(2-) (3) cluster possesses 10 delocalized π electrons, closely analogous to the bonding pattern of the aromatic naphthalene C10H8. The B6S6(-) (2) and B6S6 (1) species are readily obtained upon removal of one or two π electrons from B6S6(2-) (3). The results build a new analogous relationship between boron sulfide clusters and their PAH counterparts. The B6S6(-) (2) monoanion and B6S6(2-) (3) dianion can be effectively stabilized in neutral LiB6S6 and Li2B6S6 salts, respectively.
authors.affiliation: Department of Chemistry and Chemical Engineering, Binzhou University, Binzhou 256603, Shandong, People's Republic of China.
authors.forename: Da-Zhi
authors.initials: DZ
authors.lastname: Li
authors.affiliation: Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, Shanxi, People's Republic of China.
authors.forename: Hui
authors.initials: H
authors.lastname: Bai
authors.affiliation: Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, Shanxi, People's Republic of China.
authors.forename: Ting
authors.initials: T
authors.lastname: Ou
authors.affiliation: Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, Shanxi, People's Republic of China.
authors.forename: Qiang
authors.initials: Q
authors.lastname: Chen
authors.affiliation: Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, Shanxi, People's Republic of China.
authors.forename: Hua-Jin
authors.initials: HJ
authors.lastname: Zhai
authors.affiliation: Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, Shanxi, People's Republic of China.
authors.forename: Si-Dian
authors.initials: SD
authors.lastname: Li