Fluorescence excitation and excited state intramolecular proton transfer of jet-cooled naphthol derivatives: part 2. 2-Hydroxy–1-naphthaldehyde

Abstract

The S₁ ← S₀ fluorescence excitation spectrum of jet-cooled 2-hydroxy–1-naphthaldehyde (2H1N) with origin at 26 668 cm⁻¹ has been measured. Nine totally symmetric modes and three non-totally symmetric modes have been assigned in the excitation spectrum. Ab initio calculations indicate that 2H1N undergoes a planarity change upon excitation, which may account for the unusual intensity of non totally symmetric vibrational modes in the excitation spectrum. A number of low intensity features were observed on the low energy side of the origin which have been assigned to the 2H1N dimer rather than different ground state confomers of 2H1N. The origin of the S₁ ← S₀ electronic transition of the dimer lies at ∼26 401 cm⁻¹; combinations of two low frequency intermolecular modes of the dimer (59 cm⁻¹ and 17 cm⁻¹) were also observed. The occurrence of excited state intramolecular proton transfer (ESIPT) in 2H1N cannot be proven on the basis of this work. A comparison of the (photo)physical properties of 2H1N with 1-hydroxy-2-naphthaldehyde (1H2N) [A. McCarthy and A.A. Ruth, PCCP, 2011, 13, 7485–7499 (Part 1)], however, indicate the plausibility of an ESIPT process in 2H1N. The strength of the intramolecular hydrogen bond (IMHB) in 2H1N was computed as ∼10.6 kcal/mol, a value comparable to the IMHB strength of 1H2N. The establishment of a lower limit on the state lifetimes of 2H1N, of ∼1.8 ps, indicates that any proposed ESIPT reaction in 2H1N may not proceed barrierlessly. Above an excess energy of ∼1000 cm⁻¹, the intensity of the fluorescence excitation spectrum reduces significantly, indicating the onset of a non-radiative decay mechanism.