Institue of Molecular Sciences, Shanxi University, Taiyuan 030001, Shanxi, People's Republic of China.
J Mol Model. 2013 Mar;19(3):1195-204. doi: 10.1007/s00894-012-1640-8. Epub 2012 Nov 16.
Calculations performed at the ab initio level using the recently reported planar concentric π-aromatic B(18)H(6)(2+)(1) [Chen Q et al. (2011) Phys Chem Chem Phys 13:20620] as a building block suggest the possible existence of a new class of B(3n)H(m) polycyclic aromatic hydroboron (PAHB) clusters-B(30)H(8)(2), B(39)H(9)(2-)(3), B(42)H(10)(4/5), B(48)H(10)(6), and B(72)H(12)(7)-which appear to be the inorganic analogs of the corresponding C(n)H(m) polycyclic aromatic hydrocarbon (PAHC) molecules naphthalene C(10)H(8), phenalenyl anion C(13)H(9)(-), phenanthrene/anthracene C(14)H(10), pyrene C(16)H(10), and coronene C(24)H(12), respectively, in a universal atomic ratio of B:C = 3:1. Detailed canonical molecular orbital (CMO), adaptive natural density partitioning (AdNDP), and electron localization function (ELF) analyses indicate that, as they are hydrogenated fragments of a boron snub sheet [Zope RR, Baruah T (2010) Chem Phys Lett 501:193], these PAHB clusters are aromatic in nature, and exhibit the formation of islands of both σ- and π-aromaticity. The predicted ionization potentials of PAHB neutrals and electron detachment energies of small PAHB monoanions should permit them to be characterized experimentally in the future. The results obtained in this work expand the domain of planar boron-based clusters to a region well beyond B(20), and experimental syntheses of these snub B(3n)H(m) clusters through partial hydrogenation of the corresponding bare B(3n) may open up a new area of boron chemistry parallel to that of PAHCs in carbon chemistry.
使用最近报道的平面同心π-芳香 B(18)H(6)(2+) [Chen Q 等人，(2011)Phys Chem Chem Phys 13:20620]作为构建块，在从头算水平上进行的计算表明，可能存在一类新的 B(3n)H(m)多环芳香硼氢化物 (PAHB) 簇-B(30)H(8)(2)、B(39)H(9)(2-)、B(42)H(10)(4/5)、B(48)H(10)(6)和 B(72)H(12)(7)-它们似乎是相应的 C(n)H(m)多环芳烃 (PAHC) 分子萘 C(10)H(8)、苯并菲阴离子 C(13)H(9)(-)、菲 C(14)H(10)、芘 C(16)H(10)和冠状物 C(24)H(12)的无机类似物，其通用原子比为 B:C = 3:1。详细的正则分子轨道 (CMO)、自适应自然密度分区 (AdNDP) 和电子定域函数 (ELF) 分析表明，由于它们是硼扭结片的氢化片段[Zope RR, Baruah T (2010)Chem Phys Lett 501:193]，这些 PAHB 簇具有芳香性，并表现出 σ-和 π-芳香性的形成。PAHB 中性体的预测电离势和小 PAHB 单核阴离子的电子离解能应该允许它们在未来通过实验进行表征。这项工作的结果将平面硼基簇的范围扩展到远超出 B(20)的区域，并且通过相应的裸露 B(3n)的部分氢化来合成这些扭结 B(3n)H(m)簇可能会开辟硼化学的一个新领域，与碳化学中的 PAHC 平行。
