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 language | English |
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Number of pages | 7 |
Journal | Chemical Science |
Early online date | 23 Aug 2024 |
DOIs | |
Publication status | E-pub ahead of print - 23 Aug 2024 |