Photophysical properties and fluorosolvatochromism of D–π–A thiophene based derivatives

Abstract

Solvation-dependent photophysical properties of two push–pull thiophene-based compounds with donor–π–acceptor (D–π–A) structures were investigated using absorption, fluorescence emission and time resolved spectroscopy, and supported by different solvation models. Intramolecular charge transfer characteristics of the structurally similar 2-fluoro-4-(5-(4-methoxyphenyl)thiophen-2-yl)benzonitrile (MOT) and 4-(5-(4-(dimethylamino)phenyl)thiophen-2-yl)-2-fluorobenzonitrile (DMAT) were investigated. Significant enhancement of intramolecular charge transfer strength has been observed through molecular structure modification of the electron donating group from a methoxy to dimethylamine group. Ground state absorption spectra show a small red shift of about 10 nm and 18 nm while the fluorescence emission spectra show a large red shift of about 66 nm and 162 nm on changing from the nonpolar cyclohexane to the aprotic polar DMSO for MOT and DMAT, respectively. Dipole moment change from the ground state to the charge transfer excited state is calculated to be 6.6 D in MOT and 9.0 D in DMAT. The fluorescence quantum yield, fluorescence lifetime and the derived radiative and non-radiative rate constants were found to be better correlated to the emission energy rather than any of the solvent properties. Three multi-parametric relationships were used in the interpretation of the specific versus non-specific solute–solvent interactions, namely, Kamlet–Taft, Catalán and Laurence et al. models. The findings of these approaches are used to extract useful information about different aspects of solvent effects on the photophysical properties of the two studied compounds. Kamlet–Taft solvatochromic model indicates that non-specific interactions are dominant in controlling the photophysical properties. Catalán's solvent dipolarity/polarizability parameter is found to play a significant role in solvatochromic behaviour which is also designated by the Laurence model.