Absolute configuration of a [1]rotaxane determined from vibrational and electronic circular dichroism spectra

Andrew R Puente; Adrien Bessaguet; Noël Pairault; Grégory Pieters; Jeanne Crassous; Prasad L Polavarapu; Isabelle Opalinski; Sébastien Papot

doi:10.1002/chir.23365

Absolute configuration of a [1]rotaxane determined from vibrational and electronic circular dichroism spectra

Chirality. 2021 Nov;33(11):773-782. doi: 10.1002/chir.23365. Epub 2021 Sep 29.

Authors

Andrew R Puente¹, Adrien Bessaguet², Noël Pairault², Grégory Pieters³, Jeanne Crassous⁴, Prasad L Polavarapu¹, Isabelle Opalinski², Sébastien Papot²

Affiliations

¹ Department of Chemistry, Vanderbilt University, Nashville, Tennessee, USA.
² Institut de Chimie des Milieux et des Matériaux de Poitiers (IC2MP), Groupe "Système Moléculaires Programmés", UMR CNRS 7285, Université de Poitiers, Poitiers Cedex 9, France.
³ Université Paris-Saclay, CEA, INRAE, Département Médicaments et Technologies pour la Santé (DMTS), SCBM, 91191 Gif-sur-Yvette, France, Gif-sur-Yvette, France.
⁴ Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, Campus de Beaulieu, Univ Rennes, Rennes Cedex, France.

PMID: 34590354
DOI: 10.1002/chir.23365

Abstract

The experimental vibrational circular dichroism (VCD) and electronic circular dichroism (ECD) spectra were measured for the enantiomers of [1]rotaxane 1. These experimental spectra have been analyzed using predicted VCD and ECD spectra for (S, R_mp ) or (S, S_mp ) diastereomers using density functional theory. This comparison allowed for a definitive assignment of the absolute configuration of 1.

Keywords: Rotaxane; absolute configuration; density functional theory; electronic circular dichroism; mechanical planar chirality; vibrational circular dichroism.