Effects of donor and acceptor substituents on the photophysics of 4-ethynyl-2,1,3-benzothiadiazole derivatives†

Abstract

The present work explores the photophysical, electrochemical, and fluorescence polarization properties of a group of π-conjugated phenylethynyl-2,1,3-benzothiadiazole derivatives (BTDs) bearing different electron-donating (ED) or electron-withdrawing (EW) substituents at the para position of the phenylethynyl moiety. The BTDs were synthesized through the Sonogashira cross-coupling reaction between 4-bromo-2,1,3-benzothiadiazole and the respective para-substituted phenylethynyl derivatives. The BTDs with the EW-substituents show relatively weak solvatochromic behavior, while the BTDs with the strong ED-substituents like methoxy and N,N-dimethylamino-based substituents (BTDPhOMe and BTDPhNMe₂) exhibit a pronounced solvatochromic behavior. The change in dipole moments in the excited states of the derivatives was calculated using Lippert–Mataga plots. The conclusions drawn on the spectral behavior of the molecules could be rationalized by TD-DFT calculations involving electron density difference (EDD) maps that correlate with the ICT characteristics of the molecules. The experimental and theoretical calculations reveal that the BTDs with the strong ED-substituents (strong push–pull type BTDs) have a strong ICT character in the excited state. These strong push–pull type BTDs show high fluorescence quantum yield (Φ_F) in apolar solvents and low Φ_F in polar solvents. In contrast, the BTDs with the weak ED-substituents (weak push–pull type BTDs) and EW-substituents (pull–pull type BTDs) have a weaker ICT character with low Φ_F in apolar and high Φ_F in polar solvent media. There is good a agreement among the HOMO–LUMO band gaps obtained from absorption spectroscopy and electrochemical studies and theoretical calculations. The fluorescence anisotropy measurement in the glycerol medium shows that the studied BTDs generally exhibit higher sensitivity towards microviscosity than the traditional DPH fluorescence anisotropy probe.