Intense chirality induction in nitrile solvents by a helquat dye monitored by near resonance Raman scattering

Abstract

Chirality induction phenomena attract attention because of their relevance to intermolecular interactions encountered in living matter. Usually, such effects are weak. However, enantiomers of a [6]helquat dye were found to induce exceptionally strong chirality in several achiral solvents containing nitrile groups. This effect was observable as an intense Raman optical activity (ROA) induced in acetonitrile, acetonitrile-d₃, and liquid hydrogen cyanide solvents. The observation was verified by measurement of both helquat enantiomers which provided mirror image ROA spectra. Theoretical analysis indicated that the 532 nm laser excitation light was in a near resonance with electronic transitions of the dye, which made the effect observable in very dilute solutions (1 : 200 000 helquat to nitrile ratio) and thus the phenomenon can be generally useful in analytical chemistry.