title: The Clar Structure in Inorganic BN Analogues of Polybenzenoid Hydrocarbons: Does it Exist or Not?
abstract: The Clar structure of polybenzenoid hydrocarbons (PBHs) have attracted considerable interest of both theoretical and experimental chemists since it was proposed in the 1950s. However, it remains unclear whether the Clar structure could exist in inorganic PBHs, the boron nitride (BN) analogues where the alternate boron and nitrogen atoms are used to replace the carbon atoms of PBHs. Here, we carry out thorough density functional theory (DFT) calculations to probe the possibility of Clar structures in BN analogues of PBHs. A strong correlation (r(2) =0.975) between the ring number (n=3-10) of BN analogues of [n]acenes and energy differences between the most and least stable isomers is identified, suggesting the existence of Clar structures in inorganic PBHs. In addition, the slightly weaker correlations in comparison to that (r(2) =0.989) of the organic PBHs is rationalized by the reduced aromaticity, which is revealed by two aromatic indices: ELFπ and SCI.
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, Fujian, P. R. China.
authors.forename: Jingjing
authors.initials: J
authors.lastname: Wu
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, Fujian, P. R. China. jun.zhu@xmu.edu.cn.
authors.forename: Jun
authors.initials: J
authors.lastname: Zhu
keywords: Clar structure; aromaticity; density functional calculations; electron localization function; six-center index