Anstöter, C.S. orcid.org/0000-0002-3412-2511 and Fowler, P.W. orcid.org/0000-0003-2106-1104 (2025) Perturbing pentalene: aromaticity and antiaromaticity in a non‐alternant polycyclic aromatic hydrocarbon and BN‐heteroanalogues. ChemPhysChem. e202401069. ISSN 1439-4235
Abstract
Pentalene (C8H6) and NN- and BB-bridged heterocyclic analogues (BN)4H6, derived by replacement of CC pairs with BN, are taken as paradigms for tuning of ring-current (anti)aromaticity by variation of mathematical equation charge, electronegativity and substitution pattern. Ab initio calculation of maps for the mathematical equation current density induced in these model systems by a perpendicular external magnetic field exhibits the full range of tropicity, from diatropic aromatic to nonaromatic to paratropic antiaromatic, with a ready rationalisation in terms of an orbital model. Further calculations on systems of varying charge in which these motifs are embedded in extended PAH systems with naphthalene and phenanthrene ‘clamps’ show promise for switching between current patterns and related opto-electronic properties. Particular sensitivity to charge is found for the experimentally accessible NN-bridged heteropentalene hybrids.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2025 The Authors. ChemPhysChem published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. http://creativecommons.org/licenses/by/4.0/ |
Keywords: | Ab initio calculations; antiaromaticity; aromaticity; current-density maps; ipsocentric; ring currents; selection rules; symmetry |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 25 Mar 2025 14:43 |
Last Modified: | 25 Mar 2025 14:43 |
Status: | Published online |
Publisher: | Wiley |
Refereed: | Yes |
Identification Number: | 10.1002/cphc.202401069 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:224789 |