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Steric and electronic control of 1,3-dipolar cycloaddition reactions in carbon nanotube nanoreactors

Miners, Scott A.; Fay, Michael W.; Baldoni, Matteo; Besley, Elena; Khlobystov, Andrei N.; Rance, Graham A.

Authors

Scott A. Miners

Matteo Baldoni

ELENA BESLEY Elena.Besley@nottingham.ac.uk
Professor of Theoretical Computational Chemistry



Abstract

The use of single-walled carbon nanotubes as effective nanoreactors for preparative bimolecular reactions has been demonstrated for the first time. We show that the extreme spatial confinement of guest reactant molecules inside host carbon nanotubes increases the regioselectivity for 1,4-triazole in thermally initiated azide–alkyne cycloaddition reactions. Through comparison of the internal dimensions of the nanotube and the steric bulk of the reactants, we demonstrate that the formation of the more linear 1,4-regioisomer can be enhanced by up to 55% depending on the extent of spatial restrictions imposed within the nanoreactors. Furthermore, through systematic variation of the substituents in the para-position of the alkyne reactants, we reveal the unexpected influence of the reactants’ electronic properties on the regioselectivity of reactions within nanoreactors, which act to either oppose or promote the preferential formation of the 1,4-regioisomer induced by steric effects, reflecting the unique ability of carbon nanotubes to stabilize the dipole moment of confined reactants. Thus, we show that the observed regioselectivity of azide–alkyne cycloaddition reactions confined within carbon nanotube nanoreactors reflects a subtle interplay between both steric and electronic factors.

Journal Article Type Article
Publication Date Mar 14, 2019
Journal Journal of Physical Chemistry C
Print ISSN 1932-7447
Electronic ISSN 1932-7455
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 123
Issue 10
Pages 6294-6302
APA6 Citation Miners, S. A., Fay, M. W., Baldoni, M., Besley, E., Khlobystov, A. N., & Rance, G. A. (2019). Steric and electronic control of 1,3-dipolar cycloaddition reactions in carbon nanotube nanoreactors. Journal of Physical Chemistry C, 123(10), 6294-6302. https://doi.org/10.1021/acs.jpcc.9b01190
DOI https://doi.org/10.1021/acs.jpcc.9b01190
Keywords General energy; Physical and theoretical Chemistry; Electronic, optical and magnetic materials; Surfaces, coatings and films
Publisher URL https://pubs.acs.org/doi/10.1021/acs.jpcc.9b01190
Additional Information This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.jpcc.9b01190

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