Solvent effect of fluorescence on/off switching of diarylethene linked to excited-state intramolecular proton transfer fluorophore

Abstract

Efficient fluorescence on/off switching of a dyad consisting of a photochromic diarylethene and a fluorescence dye based on excited state intramolecular proton transfer (ESIPT) was designed and demonstrated. Diarylethenes linked to (2-(2-methoxy-5-methylphenyl)benzothiazol-6-yl)- and (2-(2-hydroxy-5-methylphenyl)benzothiazol-6-yl)-9,9-dioctylfluorene moieties (1a and 2a, respectively) exhibited fluorescence on/off switching upon alternating irradiation with ultraviolet and visible light in various solvents. The fluorescence on/off contrast of 2a was found to be higher than that of 1a in n-hexane because the overlap integral between the absorption spectrum of the diarylethene closed-ring form and the fluorescence spectrum of 2a is larger than that of 1a. Diarylethene 2a exhibited green fluorescence with large Stokes shift in n-hexane, which is ascribed to the ESIPT process from the enol form to the keto form. In contrast, the fluorescence of 2a in N,N-dimethylsulfoxide (DMSO) was mainly observed as blue fluorescence from enol form, while diarylethene 1a exhibited blue fluorescence in n-hexane and DMSO. The fluorescence on/off contrast of 2a in n-hexane was higher than that in DMSO because of the difference in the spectral overlaps in n-hexane and DMSO.