ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Efficient excited-state proton transfer in neutral acid–base clusters α-naphthol⋅Bn has been detected and studied by a combination of laser spectroscopic techniques (resonant two-photon ionization, fluorescence excitation, and emission spectroscopy). S1 state proton transfer was observed for B=NH3 and n≥4, as evidenced by several criteria: (a) large red shift and substantial broadening of the R2PI spectra of the n≥4 clusters relative to those of the bare α-naphthol and smaller clusters; (b) very large Stokes shift (∼8000 cm−1) of the emission spectra of the n≥4 clusters; (c) complete broadening of the fluorescence emission band for the n≥4 clusters; and (d) a striking similarity of the emission band position and width of the latter spectra to the emission spectrum of the α-naphtholate anion in basic aqueous solution. No proton-transfer reaction was observed for small solvent clusters with B=NH3 and n≤3, nor for any of the pair complexes studied, which involve a single base partner [B=triethylamine, 3-dimethylamino-1-aminopropane, 1,4-bis(dimethylamino)butane] which we have studied so far. This behavior illustrates the difficulty of achieving charge separation in neutral gas-phase complexes or clusters. A critical gas-phase proton affinity PAcrit =248±3 kcal/mol was determined for proton transfer to take place in the α-naphthol⋅Bn (or base B) system.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.453820
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