Electrochemical and Solvent-Mediated Visible-to-Near-Infrared Spectroscopic Switching of Benzoselenadiazole Fluorophores.

A series of electronic push-pull, pull-pull, and push fluorophores has been prepared from a benzoselenadiazole core so that their spectroscopic, electrochemical, spectro-electrochemical, and spectro-electrofluorescence properties could be examined. The emission wavelengths and fluorescence quantum yields (Φ ) of the N,N-dimethyl fluorophores were contingent on the solvent polarity and they ranged from 615 to 850 nm in aprotic solvents. The positive solvatochromism and the quenched Φ in polar solvents were consistent with an intramolecular charge-transfer state (ICT). Meanwhile, a locally excited state (LE) was assigned in nonpolar solvents from the blue-shifted emission and high Φ . The N,N-dimethylamine fluorophores examined could be both electrochemically oxidized and reduced, whereas the symmetric dinitro pull-pull derivative could be only reversibly reduced. Courtesy of their electrochemical reversibility, the fluorophores could reversibly change color from yellow to blue with an applied potential in addition to switching off their emission. The absorption of the electrochemically generated intermediates of the N,N-dimethyl derivatives spanned 500 nm over the visible and the NIR regions. The colors could be switched for upwards of two hours with applied potential, illustrating their potential use as electroactive materials in electrochromic devices.