Chirality effects in gas-phase spectroscopy and photophysics of molecular and ionic complexes: contribution of low and room temperature studies

Abstract

This review focuses on chirality effects in spectroscopy and photophysics of chiral molecules or protonated ions, and their weakly bound complexes, isolated in the gas phase. Low-temperature studies in jet-cooled conditions allow disentangling the different interactions at play and shed light on the ancillary interactions responsible for chiral recognition, like OH…π or CH…π, which would be blurred at room temperature. The consequences of these interactions on chiral recognition in condensed phase are described, as well as the influence of higher energy conformers, which can be accessed in room-temperature experiments. The role of kinetic effects and solvation in jet-cooled experiments is discussed. Last, examples of dramatic chirality effects in photo-induced dissociation are given.

Keywords:

• chirality
• chiral recognition
• hydrogen bond
• laser spectroscopy
• supersonic expansion
• mass spectrometry

Acknowledgements

Thanks are due to the co-workers and colleagues for their contributions to this work, as reflected in the list of references. I especially acknowledge the decisive contribution of Dr K. Le Barbu-Debus and a long-going collaboration with Prof Dr M. Suhm. Support from CNRS, Univ. Paris Sud, and ANR is acknowledged (Grant ANR-08-BLAN-0158), as well as computer time allowances by DI Univ. Paris Sud. We acknowledge the use of the computing facility cluster GMPCS of the LUMAT federation (FR LUMAT 2764). The research described here has been supported by Triangle de la Physique contract Dichromol no. 2007-025T.

Notes

1. Hydrogen-bonded cycles will be denoted by Cn where n stands for the total number of atoms involved in the ring.