Tuning the photoinduced electron-transfer thermodynamics in 1,3,5-triaryl-2-pyrazoline fluorophores: X-ray structures, photophysical characterization, computational analysis, and in vivo evaluation

Abstract

A series of donor-substituted 1,3,5-triaryl-2-pyrazoline fluorophores were structurally characterized by X-ray analysis, and their photophysical properties studied by steady-state absorption and emission spectroscopy. The photoinduced electron-transfer thermodynamics of the derivatives was estimated on the basis of the spectroscopic data and redox potentials of the fluorophores. The aryl substituents in the 1- and 3-position of the pyrazoline ring influence the photophysical properties of the fluorophores in distinctly different ways. The excited-state equilibrium energy DeltaE(00) is primarily influenced by changes of the substituent in the 1-position, whereas the reduction potential of the fluorophore is essentially determined by the 3-aryl group. Density functional calculations were used to probe the electronic structure and energy ordering of the emissive and the electron-transfer state. The results from the computational analysis agree qualitatively well with the experimental data. In addition, we have evaluated a water soluble pyrazoline derivative in vivo as a potential intracellular pH probe. Membrane permeability, low toxicity, and high quantum yield render the fluorophore attractive for biological applications.