Excited-state proton transfer (ESPT) reactions of 5-cyano-2-naphthol (5CN2) and 5,8-dicyano-2-naphthol (DCN2) were investigated in protic ionic liquids (PILs) composed of quaternary ammonium (NnnnH+) (n = 2, 4, or 8) and hexanoate (C5H11COO-) using time-resolved fluorescence spectroscopy. The effects of the number of alkyl carbons in the cation and the basicity of the anion on the reaction yield and dynamics were examined. In a series of [NnnnH][C5H11COO], fluorescence from the hydrogen-bonding complex (AHBX-*) of a proton-dissociated form (RO-*) with a solvent acid in the electronic excited state was observed between the fluorescence bands of an acidic form (ROH*) and an anionic form (RO-*) as in the case of [N222H][CF3COO] (Fujii et al., J. Phys. Chem B, 2017, 121, 6042). The yield, formation rate, and decay rate of AHBX-* were assessed by the steady-state fluorescence intensity ratio of AHBX-* to RO-* and by analysis of the time-resolved fluorescence spectra within several tens of nanoseconds. The stability of AHBX-* was significantly different from that in [N222H][CF3COO] and depended on the number of alkyl carbons in the cation. The formation of AHBX-* was quite fast compared to the case in [N222H][CF3COO] and almost close to the excitation pulse width. Excitation wavelength dependence of the fluorescence dynamics was observed within several hundred picoseconds for the series of [NnnnH][C5H11COO]. The origin was ascribed to the complex with solvent IL formed in the electronic ground state, as suggested by the density-functional theory (DFT) calculations.
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