Molecular Horizons - Oisin Shiels, PhD Exit Seminar

Electrostatic catalysis is a rapidly expanding area of chemistry that promises to create greener, more atom-economic, processes that rely on electrostatic fields to enhance reactions. However, since molecules are typically unaligned in bulk conditions, the highly directional nature of electrostatic interactions currently prevents widespread application. Distonic radical ions – species with spatially separated charge and radical sites ¬– overcome this experimental challenge by locking the position of an internal electric field which influences the reactivity of the radical site. In principle, this internal field can be controlled synthetically by changing the charged functional group or introducing neutral substituents to fine-tune reactivity and select for desired major products. However, our understanding of how electrostatic fields influence these reactions is still superficial, and theoretical methods that accurately predict these effects are required before electrostatic catalysis can be reliably harnessed. This presentation outlines the range of mass spectrometry and theoretical techniques developed to measure, predict, and ultimately control the electrostatic catalysis of distonic radical ion–molecule reactions in the gas-phase, and beyond.