Does excited-state proton-transfer reaction contribute to the emission behaviour of 4-aminophthalimide in aqueous media?

Abstract

4-Aminophthalimide (AP) is an extensively used molecule both for fundamental studies and applications primarily due to its highly solvent-sensitive fluorescence properties. The fluorescence spectrum of AP in aqueous media was recently shown to be dependent on the excitation wavelength. A time-dependent blue shift of its emission spectrum is also reported. On the basis of these findings, the excited-state solvent-mediated proton-transfer reaction of the molecule, which was proposed once but discarded at a later stage, is reintroduced. We report on the fluorescence behaviour of AP and its imide-H protected derivative, N-BuAP, to prove that a solvent-assisted excited-state keto-enol transformation does not contribute to the steady-state and time-resolved emission behaviour of AP in aqueous media. Our results also reveal that the fluorescence of AP in aqueous media arises from two distinct hydrogen-bonded species. The deuterium isotope effect on the fluorescence quantum yield and lifetime of AP, which was thought to be a reflection of the excited-state proton-transfer reaction in the system, is explained by considering the difference in the influence of H2O and D2O on the nonradiative rates and ground-state exchange of the proton with the solvent. Insight into photophysics: The time-resolved and time-integrated fluorescence response of 4-aminophthalimide and its derivative does not indicate photoinduced solvent-mediated intramolecular proton transfer in protic media. Two distinct types of hydrogen-bonded complex of the molecule with the solvent are identified and a new explanation for the solvent isotope effect is suggested. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.