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Vibrational circular dichroism spectroscopy for probing the expression of chirality in mechanically planar chiral rotaxanes

Vibrational circular dichroism spectroscopy for probing the expression of chirality in mechanically planar chiral rotaxanes
Vibrational circular dichroism spectroscopy for probing the expression of chirality in mechanically planar chiral rotaxanes
Mechanically interlocked molecules can exhibit molecular chirality that arises due to the mechanical bond rather than covalent stereogenic units. Developing applications of such systems is made challenging by the absence of techniques for assigning the absolute configuration of products and methods to probe how the mechanical stereogenic unit influences the spatial arrangements of the functional groups in solution. Here we demonstrate for the first time that Vibrational Circular Dichroism (VCD) can be used to not only discriminate between mechanical stereoisomers but also provide detailed information on their (co)conformations. The latter is particularly important as these molecules are now under investigation in catalysis and sensing, both of which rely on the solution phase shape of the interlocked structure. Detailed analysis of the VCD spectra shows that, although many of the signals arise from coupled oscillators isolated in the covalent sub-components, intercomponent coupling between the macrocycle and axle gives rise to several VCD bands.
1478-6524
8469-8475
Koenis, V. Mark Antonius Johannes
e959980c-a391-4fc6-a0d1-974a27058dea
Chiueze, Chima
5dd0f912-b092-41e9-96b3-3922ebaf1386
Jinks, Michael A
c8ce33cc-8ead-4763-b294-ae94ce0475d0
Nicu, Valentin P.
6629feb7-8e82-4ba0-b764-0e19d78a911c
Visscher, Lucas
44f84999-bc0f-4492-abf3-8f41af9dc1a3
Goldup, Stephen
0a93eedd-98bb-42c1-a963-e2815665e937
Bma, Wybren J.
de49c41a-606b-4f08-a34b-170808e95433
Koenis, V. Mark Antonius Johannes
e959980c-a391-4fc6-a0d1-974a27058dea
Chiueze, Chima
5dd0f912-b092-41e9-96b3-3922ebaf1386
Jinks, Michael A
c8ce33cc-8ead-4763-b294-ae94ce0475d0
Nicu, Valentin P.
6629feb7-8e82-4ba0-b764-0e19d78a911c
Visscher, Lucas
44f84999-bc0f-4492-abf3-8f41af9dc1a3
Goldup, Stephen
0a93eedd-98bb-42c1-a963-e2815665e937
Bma, Wybren J.
de49c41a-606b-4f08-a34b-170808e95433

Koenis, V. Mark Antonius Johannes, Chiueze, Chima, Jinks, Michael A, Nicu, Valentin P., Visscher, Lucas, Goldup, Stephen and Bma, Wybren J. (2020) Vibrational circular dichroism spectroscopy for probing the expression of chirality in mechanically planar chiral rotaxanes. Chemical Science, 11 (32), 8469-8475. (doi:10.1039/D0SC02485F).

Record type: Article

Abstract

Mechanically interlocked molecules can exhibit molecular chirality that arises due to the mechanical bond rather than covalent stereogenic units. Developing applications of such systems is made challenging by the absence of techniques for assigning the absolute configuration of products and methods to probe how the mechanical stereogenic unit influences the spatial arrangements of the functional groups in solution. Here we demonstrate for the first time that Vibrational Circular Dichroism (VCD) can be used to not only discriminate between mechanical stereoisomers but also provide detailed information on their (co)conformations. The latter is particularly important as these molecules are now under investigation in catalysis and sensing, both of which rely on the solution phase shape of the interlocked structure. Detailed analysis of the VCD spectra shows that, although many of the signals arise from coupled oscillators isolated in the covalent sub-components, intercomponent coupling between the macrocycle and axle gives rise to several VCD bands.

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Accepted/In Press date: 23 July 2020
e-pub ahead of print date: 23 July 2020
Published date: 21 August 2020

Identifiers

Local EPrints ID: 442731
URI: http://eprints.soton.ac.uk/id/eprint/442731
ISSN: 1478-6524
PURE UUID: d0e4fc50-eab7-4724-abdd-524bfc9dcc1a
ORCID for Stephen Goldup: ORCID iD orcid.org/0000-0003-3781-0464

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Date deposited: 24 Jul 2020 16:30
Last modified: 28 Apr 2022 02:12

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Contributors

Author: V. Mark Antonius Johannes Koenis
Author: Chima Chiueze
Author: Michael A Jinks
Author: Valentin P. Nicu
Author: Lucas Visscher
Author: Stephen Goldup ORCID iD
Author: Wybren J. Bma

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