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Specific microsolvation triggers dissociation-mediated anomalous red-shifted fluorescence in the gas phase.

Ion-depletion IR spectroscopy has revealed that at least two water molecules are required in complexes with 4-(dimethylamino)benzoic acid methyl ester (DMABME) for anomalous red-shifted fluorescence to occur in the gas phase. Through the use of high-level quantum-chemical calculations, two experimentally observed isoenergetic isomers are assigned to complexes in which a water dimer is hydrogen-bonded either to the carbonyl oxygen of the ester function or to the amino nitrogen. Surprisingly, computed IR spectra reveal that the N-bonded isomer is responsible for the observed red-shifted fluorescence. For an explanation, the mechanism of twisted intramolecular charge-transfer (TICT) formation and energy dissipation is investigated in detail. In general, for red-shifted fluorescence to occur, the N-bonded complexes must be able to dissipate energy, which in the gas phase can only happen nonradiatively via fragmentation. Arguments are given that only the N-bonded isomer photodissociates rapidly enough into free DMABME and a water dimer as a result of the immediate repulsion between the amino nitrogen and the water dimer in the TICT state. The O-bonded isomer, on the other hand, stays intact because the hydrogen bond is strengthened by additional electrostatic attraction in the ICT state. Furthermore, an experiment to further corroborate that mechanism is suggested.