Abstract
AbstractAfter resonant two‐photon ionization of mixed clusters of substituted aromatics with polar and unpolar solvents we observed very selective intracluster relaxation reactions. They are assumed to take place in the cationic complexes. The selectivity of a nucleophilic substitution reaction of halogenated benzenenes with nucleophiles is rationalized by different isomeric structures of the neutral aggregates. Proton transfer from ionized methylated benzenes to polar solvents is found to be governed by the solvent's proton solvation energetics. Electron transfer, at present studied only for ether compounds as solvent, takes place, if the ionization potential of the solute is larger than of the solvent.
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