Möbius and Hückel Cyclacenes with Dewar and Ladenburg Defects

Hanson-Heine, Magnus W.D.; Hirst, Jonathan D.

Abstract

Copyright © 2020 American Chemical Society. Cyclacene nanobelts have not been synthesized in over 60 years and remain one of the last unsynthesized building blocks of carbon nanotubes. Recent work has predicted that Hückel-cyclacenes containing Dewar benzenoid ring isomers are the most stable isomeric forms for several of the smaller sizes of cyclacene belts. Here, we give a more complete picture of the isomers that are possible within these nanobelt systems by simulating embedded Ladenburg (prismane) benzenoid rings in Hückel-[n]cyclacenes (n = 5-14) and embedded Dewar benzenoid rings in twisted Möbius-[n]cyclacenes (n = 9-14). The Möbius-[9]cyclacene isomer containing one Dewar benzenoid defect and the Hückel-[5]cyclacene isomer containing two maximally spaced Ladenburg benzenoid defects are found to be more stable than their conventional Kekulé benzenoid ring counterparts. The isomers that contain Dewar and Ladenburg benzenoid rings have larger electronic singlet-triplet energy gaps and lower polyradical character when compared with the conventional isomers.

Citation

Hanson-Heine, M. W., & Hirst, J. D. (2020). Möbius and Hückel Cyclacenes with Dewar and Ladenburg Defects. Journal of Physical Chemistry A, 124(26), 5408-5414. https://doi.org/10.1021/acs.jpca.0c04137

• Journal Article Type: Article
• Acceptance Date: Jun 14, 2020
• Online Publication Date: Jun 14, 2020
• Publication Date: Jul 2, 2020
• Deposit Date: Jun 19, 2020
• Publicly Available Date: Jun 15, 2021
• Journal: Journal of Physical Chemistry A
• Print ISSN: 1089-5639
• Electronic ISSN: 1520-5215
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 124
• Issue: 26
• Pages: 5408-5414
• DOI: https://doi.org/10.1021/acs.jpca.0c04137
• Keywords: Physical and Theoretical Chemistry
• Public URL: https://nottingham-repository.worktribe.com/output/4678427
• Publisher URL: https://pubs.acs.org/doi/10.1021/acs.jpca.0c04137
• Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry A ,copyright ©American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpca.0c04137