Topological Ring Currents and Bond Currents in Some Neutral and Anionic Altans and Iterated Altans of Corannulene and Coronene.
Mallion, Roger B
The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory
American Chemical Society
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Dickens, T., & Mallion, R. B. (2018). Topological Ring Currents and Bond Currents in Some Neutral and Anionic Altans and Iterated Altans of Corannulene and Coronene.. The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory, 122 (38), 7666-7678. https://doi.org/10.1021/acs.jpca.8b06862
The novel series of conjugated systems called altans, defined nearly a decade ago, was subsequently extended to multiple ("iterated") altans, and their magnetic properties were calculated by Monaco and Zanasi using the ab initio ipso-centric formalism. Such properties of the single ("mono") altans of corannulene and coronene, calculated by this sophisticated ab initio approach, had earlier been compared with those calculated via the rudimentary Hückel-London-Pople-McWeeny (HLPM) method-a parameter-free topological, quasi graph-theoretical approach requiring knowledge only of the conjugated system's molecular graph and the areas of its constituent rings. These investigations are here extended to double and triple altans. HLPM bond currents in several neutral mono altans are found to differ from those in the corresponding dianion only in those bonds that lie on the structures' perimeters, while the HLPM bond currents in all bonds in the neutral double and triple altans of corannulene and coronene are precisely the same as in the respective dianions. Some rationalization of these unexpected phenomena is offered in terms of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) nature of the role played by the lone nonbonding orbital in each of the neutral species and its respective dianion.
External DOI: https://doi.org/10.1021/acs.jpca.8b06862
This record's URL: https://www.repository.cam.ac.uk/handle/1810/285380