Interplay of Aromaticity and Antiaromaticity in N‑Doped Nanographenes

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 124; no. 4; pp. 695 - 703
• Main Authors: Benkyi, Isaac, Staszewska-Krajewska, Olga, Gryko, Daniel T, Jaszuński, Michał, Stanger, Amnon, Sundholm, Dage
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 30.01.2020
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.9b11315

The aromaticity of three nonplanar, fully conjugated aza-nanographenes built around a pyrrolo­[3,2-b]­pyrrole core is assessed through the application of two different computational proceduresGIMIC and NICS. We examine the calculated magnetically induced current densities (GIMIC) and nucleus-independent chemical shifts (NICS). The structural differences between these three apparently similar molecules lead to significantly different aromatic properties. GIMIC analysis indicates that the peripheral diatropic ring current of 3.9 nA/T for the studied bowl-shaped diaza-nanographene is the strongest, followed by the double [6]­helicene which lacks seven-membered rings, and is practically nonexistent for the double [5]­helicene possessing seven-membered rings. The biggest difference however is that in the two not-fully-fused molecules, the central pyrrole rings possess a significant diatropic current of about 4.1 nA/T, whereas there is no such current in the diaza-nanographene. Moreover, the antiaromaticity of the seven-membered rings is increasing while moving from double [5]­helicene to diaza-nanographene (from −2.4 to −6.0 nA/T). The induced currents derived from NICSπ,zz -XY-scan analysis for all of the studied systems are in qualitative agreement with the GIMIC results. Subtle differences may originate from σ-electron currents in GIMIC or inaccuracy of NICSπ,zz values due to the nonplanarity of the systems, but the general picture is similar.