Institute of Organic Chemistry and Biochemistry, Flemingovo náměstí 2, 16610, Prague, Czech Republic.
Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada.
Angew Chem Int Ed Engl. 2020 Dec 1;59(49):21895-21898. doi: 10.1002/anie.202011146. Epub 2020 Oct 19.
Previously, we and other laboratories have reported an unusual and strong Raman optical activity (ROA) induced in solvents by chiral dyes. Various theories of the phenomenon appeared, but they were not capable of explaining fully the observed ROA band signs and intensities. In this work, an analysis based both on the light scattering theory and dedicated experiments provides a more complete understanding. For example, double-cell magnetic circular dichroism and magnetic ROA experiments with copper-porphyrin complex show that the induced chirality is observed without any contact of the solvents with the complex. The results thus indicate that a combination of electronic circular dichroism (ECD) with the polarized Raman scattering is responsible for the effect. The degree of circularity of solvent vibrational bands is a principal molecular property participating in the event. The insight and the possibility to predict the chirality transfer promise future applications in spectroscopy, chemical analysis and polarized imaging.
先前,我们和其他实验室已经报道了在溶剂中由手性染料引起的异常强的拉曼光学活性(ROA)。该现象出现了各种理论,但它们不能完全解释观察到的 ROA 带的符号和强度。在这项工作中,基于光散射理论和专门实验的分析提供了更全面的理解。例如,带有铜卟啉配合物的双池磁圆二色性和磁 ROA 实验表明,在溶剂与配合物没有任何接触的情况下观察到了诱导的手性。因此,结果表明电子圆二色性(ECD)与偏振拉曼散射的组合负责该效应。溶剂振动带的圆度是参与该事件的主要分子性质。这种洞察力和预测手性转移的可能性有望在光谱学、化学分析和偏振成像中得到应用。