Room Temperature Chiral Discrimination in Paramagnetic NMR Spectroscopy

Phys Rev Lett. 2016 Apr 22;116(16):163001. doi: 10.1103/PhysRevLett.116.163001. Epub 2016 Apr 18.

Abstract

A recently proposed theory of chiral discrimination in NMR spectroscopy based on the detection of a molecular electric polarization P rotating in a plane perpendicular to the NMR magnetic field [A. D. Buckingham, J. Chem. Phys. 140, 011103 (2014)] is generalized here to paramagnetic systems. Our theory predicts new contributions to P, varying as the square of the inverse temperature. Ab initio calculations for ten Dy^{3+} complexes, at 293 K, show that, in strongly anisotropic paramagnetic molecules, P can be more than 1000 times larger than in diamagnetic molecules, making paramagnetic NMR chiral discrimination amenable to room temperature detection.