Correlated shapeshifting and configurational isomerization

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

Research output: Contribution to journalArticlepeer-review

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.
Original languageEnglish
Number of pages7
JournalChemical Science
Early online date23 Aug 2024
DOIs
Publication statusE-pub ahead of print - 23 Aug 2024

Bibliographical note

© 2024 The Author(s).

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