Structure and reactions of aliphatic bridged bifunctional radical ions: Exploring fine-tuning in radiation chemistry

Bridged bifunctional molecules of general structure X(CH₂)_nY are useful models for investigations into the effects of intra‐ and intermolecular interactions in primary radiation‐induced processes, with a number of implications for radiation chemistry, radiobiology, and molecular electronics. This short Review presents an outline of recent studies on the structure and reactivity of aliphatic bifunctional radical ions in low‐temperature matrices using EPR spectroscopy and quantum‐chemical calculations. Both EPR data and DFT calculations for radical cations show that the delocalization of charge and spin density occurs if XY or X and Y have close electronic properties. If the difference in the ionization potentials between X and Y is large, localized radical cations are observed with ground‐state properties close to those of the corresponding monofunctional species. Nevertheless, the remote second functional group may affect the photochemistry of such radical cations at a specific bridge length, probably due to intramolecular interactions in a certain conformation. The stabilization of bridged bifunctional radical anions containing two carbonyl groups was found to be very sensitive to the local environment, which may be described in terms of a microsolvation model at the MP2 level of theory. Two independent reactions pathways with excess electrons, yielding different types of localized radical anions, were demonstrated for asymmetrical bifunctional molecules. The obtained results and their implications are discussed in terms of fine‐tuning effects in radiation‐induced chemical processes in condensed phases.