Promeet Saha promeet.saha@durham.ac.uk
PGR Student Doctor of Philosophy
Rupturing aromaticity by periphery overcrowding
Saha, Promeet K.; Mallick, Abhijit; Turley, Andrew T.; Bismillah, Aisha N.; Danos, Andrew; Monkman, Andrew P.; Avestro, Alyssa-Jennifer; Yufit, Dmitry S.; McGonigal, Paul R.
Authors
Abhijit Mallick
Andrew T. Turley
Aisha Bismillah aisha.n.bismillah@durham.ac.uk
PGR Student Doctor of Philosophy
Dr Andrew Danos andrew.danos@durham.ac.uk
Senior Experimental Officer
Professor Andrew Monkman a.p.monkman@durham.ac.uk
Professor
Dr Alyssa-Jennifer Avestro alyssa.j.avestro@durham.ac.uk
Academic Visitor
Dr Dmitry Yufit d.s.yufit@durham.ac.uk
Academic Visitor
Dr Paul Mcgonigal paul.mcgonigal@durham.ac.uk
Academic Visitor
Abstract
The balance between strain relief and aromatic stabilization dictates the form and function of non-planar π-aromatics. Overcrowded systems are known to undergo geometric deformations, but the energetically favourable π-electron delocalization of their aromatic ring(s) is typically preserved. In this study we incremented the strain energy of an aromatic system beyond its aromatic stabilization energy, causing it to rearrange and its aromaticity to be ruptured. We noted that increasing the steric bulk around the periphery of π-extended tropylium rings leads them to deviate from planarity to form contorted conformations in which aromatic stabilization and strain are close in energy. Under increasing strain, the aromatic π-electron delocalization of the system is broken, leading to the formation of a non-aromatic, bicyclic analogue referred to as ‘Dewar tropylium’. The aromatic and non-aromatic isomers have been found to exist in rapid equilibrium with one another. This investigation demarcates the extent of steric deformation tolerated by an aromatic carbocycle and thus provides direct experimental insights into the fundamental nature of aromaticity.
Citation
Saha, P. K., Mallick, A., Turley, A. T., Bismillah, A. N., Danos, A., Monkman, A. P., …McGonigal, P. R. (2023). Rupturing aromaticity by periphery overcrowding. Nature Chemistry, 15(4), 516-525. https://doi.org/10.1038/s41557-023-01149-6
Journal Article Type | Article |
---|---|
Acceptance Date | Jan 26, 2023 |
Online Publication Date | Mar 6, 2023 |
Publication Date | 2023 |
Deposit Date | Apr 26, 2023 |
Publicly Available Date | Apr 26, 2023 |
Journal | Nature Chemistry |
Print ISSN | 1755-4330 |
Electronic ISSN | 1755-4349 |
Publisher | Nature Research |
Peer Reviewed | Peer Reviewed |
Volume | 15 |
Issue | 4 |
Pages | 516-525 |
DOI | https://doi.org/10.1038/s41557-023-01149-6 |
Public URL | https://durham-repository.worktribe.com/output/1175685 |
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