Chirality transfer observed in Raman optical activity spectra

Spectrochim Acta A Mol Biomol Spectrosc. 2022 Nov 15:281:121604. doi: 10.1016/j.saa.2022.121604. Epub 2022 Jul 8.

Abstract

Chirality transfer (also called induced chirality) is a phenomenon present in chiroptical spectra that manifests itself as a new band or bands of an achiral molecule interacting with a chiral one. In the Raman optical activity (ROA) spectroscopy, the bands of achiral solvents have been recently observed, but the latest papers have shown that they corresponded to the new ECD-Raman (eCP-Raman) effect. Here, we show an unambiguous example of chirality transfer observed in the ROA spectra. The spectra registered for the (1:1) mixtures of achiral benzonitrile with the enantiomers of 2,2,2-trifluoro-1-phenylethanol, 1-phenylethanol, and 1-phenylethylamine exhibited the v(CN) vibration band at about 2230 cm-1. The ROA measurements were repeated several times to ensure the reliability of the phenomenon. Calculations revealed the CN···HO or CN···HNH hydrogen bond formation accompanied by the π···π or CH···π interactions. The interaction strength was shown to be an important factor for the pronouncement of the ROA chirality transfer effect.

Keywords: Calculations; Chiral solvents; Induced chirality; ROA chirality transfer.

MeSH terms

  • Optical Rotation
  • Reproducibility of Results
  • Spectrum Analysis, Raman* / methods
  • Stereoisomerism
  • Vibration*