Correlated shapeshifting and configurational isomerization †

Maturi, William; Hussein, Burhan A.; Rylands, Mary Kate; Bismillah, Aisha N.; Wen, Yuzhen; Aguilar, Juan A.; Ayub, Rabia; Rankine, Conor D.; McGonigal, Paul R.

Abstract

Herein we demonstrate that the rapid ‘shapeshifting’ constitutional isomerization of a substituted bullvalene is influenced by the E-to-Z configurational isomerization of a remote carbamate group, giving rise to correlated motion. We find that, while the E-configurational isomer of a bulky carbamate favors the β-bullvalene constitutional isomer, a noncovalent bonding interaction within the Z-carbamate tips the equilibrium toward the γ-bullvalene form. Using DFT modelling and NMR spectroscopy, this long-range interaction is identified as being between the bullvalene core and a pendant phenyl group connected to the carbamate. Coupling the constitutional changes of a bullvalene to a reciprocal configurational isomerization through a long-range interaction in this way will allow shapeshifting rearrangements to be exploited as part of collective motion in extended structures.

Citation

Maturi, W., Hussein, B. A., Rylands, M. K., Bismillah, A. N., Wen, Y., Aguilar, J. A., Ayub, R., Rankine, C. D., & McGonigal, P. R. (online). Correlated shapeshifting and configurational isomerization †. Chemical Science, https://doi.org/10.1039/d4sc03699a

• Journal Article Type: Article
• Acceptance Date: Aug 23, 2024
• Online Publication Date: Aug 23, 2024
• Deposit Date: Sep 11, 2024
• Publicly Available Date: Sep 11, 2024
• Journal: Chemical Science
• Print ISSN: 2041-6520
• Electronic ISSN: 2041-6539
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• DOI: https://doi.org/10.1039/d4sc03699a
• Public URL: https://durham-repository.worktribe.com/output/2819407