Pancake 蟺鈥撓€ Bonding Goes Double: Unexpected 4e/All-Sites Bonding in Boron- and Nitrogen-Doped Phenalenyls

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• 作者：Yong-Hui Tian ; Bobby G. Sumpter ; Shiyu Du ; Jingsong Huang
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2015
• 出版时间：June 18, 2015
• 年：2015
• 卷：6
• 期：12
• 页码：2318-2325
• 全文大小：397K
• ISSN：1948-7185

文摘

Chemical bonding interactions are the main driving force for the formation of molecules and materials from atoms. The two-electron/multicenter pancake 蟺鈥撓€ bonding found in phenalenyl (PLY, 1) radical 蟺-dimers is intriguing due to its unconventional nature of covalent bonding for molecular aggregations and its propensity to induce unique optical, electronic, and magnetic properties. By using high-level quantum chemistry calculations, we show that the B- or N-doped PLYs (2 and 4), usually considered closed-shell and therefore trifling, can be rendered open-shell singlet by proper edge substitutions (3 and 5). The resulting two unpaired valence electrons on each molecular unit contribute to the formation of a genuine pancake-shaped 4e/all-sites double 蟺鈥撓€ bonding upon intermolecular 蟺-dimerization, in contrast to the 2e/half-sites single 蟺鈥撓€ bonding in the parent PLY 蟺-dimers. The unusual double 蟺鈥撓€ bonding motif discovered in these PLY analogues may broaden the landscape of, and find new applications for, intermolecular covalent bonding interactions.