Solvatochromism and fluoride sensing of thienyl-containing benzodiazaboroles

Abstract

Static and time-resolved fluorescence studies were carried out to investigate the photophysical properties and fluoride sensing abilities of highly fluorescent thienyl-containing 1,3-diethyl-1,3,2-benzodiazaboroles. Absorption and fluorescence spectra were measured in various solvents, showing the fluorophores to emit in the visible wavelength region with colors varying from blue to orange and quantum yields ranging between 0.21 and 1. Measured Stokes shifts of 2898 cm⁻¹ to 9308 cm⁻¹ were used to calculate the difference between excited- and ground-state dipole moments of the fluorophores. Values up to 18.8 D are of the same magnitude as for designed polarity probes such as PRODAN, supporting the idea of internal charge transfer transitions. Quenching studies with pyridine observing static and time-resolved fluorescence revealed a purely dynamic quenching mechanism and low Lewis acidity of the boron within the benzodiazaborolyl moiety compared to other triarylboranes. In contrast to this, quenching with fluoride was shown to stem from adduct formation. Reversible complexation of fluoride follows a simple mechanism for multi-functionalized benzodiazaboroles 2b and 2c, while those containing only one benzodiazaborole moiety (1 and 2a) show a more complicated behaviour, which might be explained by aggregation. Combining a benzodiazaborole group and a dimesitylborane function results in spectrally switchable fluoride sensors 3a and 3b, since the two boron sides can be deactivated for fluorescence in a stepwise manner.