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

Chemical Science
Mark A J KoenisWybren J Buma

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.

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Jun 15, 1986·Physical Review. B, Condensed Matter·J P Perdew
May 22, 2003·Journal of Computational Chemistry·E Van Lenthe, E J Baerends
Jul 10, 2009·Chemical Society Reviews·James D CrowleyRoy T McBurney
Oct 10, 2009·Angewandte Chemie·Mee-Kyung ChungMichel R Gagné
May 11, 2010·Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy·Jian ShenRoy Vaz
Mar 4, 2011·Journal of Computational Chemistry·Stefan GrimmeLars Goerigk
Nov 26, 2011·Chemical Society Reviews·Ali CoskunBartosz A Grzybowski
Dec 4, 2012·Journal of Chemical Theory and Computation·Michael GausMarcus Elstner
Feb 25, 2014·Journal of the American Chemical Society·Robert J Bordoli, Stephen M Goldup
May 13, 2014·Chirality·Valentin Paul NicuPrasad L Polavarapu
Sep 9, 2015·Chemical Reviews·Sundus Erbas-CakmakAlina L Nussbaumer
Feb 3, 2016·Journal of the American Chemical Society·Yusuf CakmakDavid A Leigh
Oct 21, 2016·Angewandte Chemie·David A Leigh
Nov 8, 2016·Chemical Communications : Chem Comm·James E M LewisStephen M Goldup
Apr 28, 2017·Chemical Society Reviews·James E M LewisStephen M Goldup
Jun 21, 2017·Angewandte Chemie·Jean-Pierre Sauvage
Oct 4, 2017·Chemical Science·Haohao FuWensheng Cai
Oct 21, 2017·Chemistry : a European Journal·Nicholas H Evans
May 26, 2018·Chemical Society Reviews·E M G JamiesonS M Goldup
Jan 1, 2016·Chemical Science·Peng LiuWensheng Cai
Sep 27, 2018·Angewandte Chemie·Michael A JinksStephen M Goldup
May 28, 2019·Journal of the American Chemical Society·Stefano CorraAlberto Credi
Jul 19, 2019·Chemistry : a European Journal·Artem OsypenkoNicolas Giuseppone
Aug 28, 2019·Angewandte Chemie·Marcel DommaschkThomas A Singleton
Dec 6, 2019·Chemical Science·Mark A J KoenisValentin P Nicu
Dec 13, 2019·Journal of Chemical Information and Modeling·Mark A J KoenisValentin P Nicu
Feb 15, 2020·Chemical Science·Marius GaedkeChristoph A Schalley

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Citations

Jun 12, 2021·Physical Chemistry Chemical Physics : PCCP·Luisa Weirich, Christian Merten
Apr 20, 2021·Physical Chemistry Chemical Physics : PCCP·Mark A J KoenisWybren Jan Buma

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Methods Mentioned

BETA
X-ray
circular dichroism

Software Mentioned

Amsterdam Density Functional ( ADF2019 )
Macromodel
Schrödinger
ADF
MATLAB

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