Fluorescence Switching with a Photochromic Auxochrome

Abstract

We synthesized a photoswitchable fluorescent probe incorporating a coumarin fluorophore and an oxazine photochrome within the same molecular skeleton. The visible illumination of this fluorophore−photochrome dyad results in the excitation of the fluorescent component only if the photochromic element is activated with ultraviolet irradiation. Indeed, the photoinduced opening of the oxazine ring bathochromically shifts the absorption of the coumarin fragment sufficiently to encourage its visible excitation with concomitant fluorescence. These operating principles translate into fluorescence photoactivation with good contrast ratio and brightness as well as short fluorescence lifetime. The modular character and relative simplicity of this synthetic strategy for the assembly of photoswitchable constructs might evolve into a general design logic for the photoregulation of the electronic structure of a given chromophore with a photochromic auxochrome.