Synthesis, photophysical characterization, and aerobic redox reactivity of electron-rich tellurorhodamine photocatalysts

Abstract

Tellurorhodamine dyes are a class of self-sensitizing chromophores that we have previously shown can photocatalytically oxidize a variety of organic and inorganic compounds with visible light, oxygen, and water. A new series of tellurorhodamine chromophores containing electron donating moieties were synthesized to explore how different electron donating groups affect photophysical properties and catalyst function. The synthesized complexes 1B, 1C, and 1D contain increasingly electron-donating substituents (Me, t-Butyl, OMe) on the xylene ring. 1A, containing an unsubstituted xylene, was synthesized for use as a control. UV-Vis spectroscopy was used to determine the photophysical properties of the dyes and for kinetic and thermodynamic studies. With visible light irradiation all dyes could be oxidized at room temperature to their corresponding telluroxides 2A, 2B, 2C, and 2D, as confirmed by mass spectroscopy. Comparative reduction studies using our previously established silane oxidation reaction showed that decreasing the electron density of the xylene moiety increased the rate of reduction, corresponding to a decrease in the experimental ΔG. 2D has the smallest energy barrier to silane oxidation, and a linear increase in rate with increasing substituent electron withdrawing nature was observed at low temperatures, and non-linearity at high temperatures.