Wavelength dependence measurements of the chiroptical properties in alanine crystals have so far been unsuccessful using conventional spectroscopic techniques. We describe our attempts to measure the wavelength dependence of the optical activity in L- and D-alanine crystals along each crystallographic axis, and to determine the absolute chirality of alanine crystals by correlating the absolute structure to the optical activity using an x-ray diffractometer and a generalized high accuracy universal polarimeter. We have succeeded in accurately measuring the optical rotatory dispersion in the <010> direction, which shows that the optical rotation of the D-alanine crystal is dextrorotatory and that of the L-alanine crystal is laevorotatory, thereby determining the absolute chirality. Furthermore, comparison with the optical activity in solution shows that the optical activity in alanine crystals is different not only in value, but also in the sign. These results have led us to conclude that the optical rotatory power in the crystalline state should not be simply the summation of molecular optical rotatory power values. We propose the necessity of a theory, which contains the contribution of molecular interactions within the crystal, in order to calculate the optical rotatory power of the crystalline state.
ASJC Scopus subject areas
- 化学 (全般)