Intramolecular charge transfer and solvation dynamics of push–pull dyes with different π-conjugated linkers

Abstract

The solvation-dependent excited state dynamics of two push–pull fluorophores with donor–π–acceptor (D–π–A) structures were investigated using steady-state and ultrafast transient absorption (TA) spectroscopy, backed by theoretical calculations. Identical D and A groups were present in both dyes, which differed only in the structure of their central π-conjugated linkers. Dye 1 features a p-phenylenediethynyl linker, while dye 2 contains a 2,5-diethynylthiophene linker. From the steady-state spectra, no appreciable shifts in absorption bands were observed, whereas large red-shifts in emission were seen with increasing solvent polarity, which indicated that the excited states were more polar than the ground state. Theoretical calculations support charge transfer from the triphenylamine (TPA) donor to the pentafluorosulfanyl (SF₅) acceptor via π-conjugated linkers to form an intramolecular charge transfer (ICT) state. TA spectra revealed that a solvation-stabilized conformationally relaxed intramolecular charge transfer (ICT′) state was formed in polar solvents, but only an ICT state was observed in nonpolar solvent. The SE band was quenched within 1 ps in high-polarity solvent, which corresponds to the low fluorescence quantum yield. It can be concluded that the dye with the p-phenylenediethynyl π-linker (i.e., dye 1) exhibits a larger degree of ICT than the thiophene analogue (i.e., dye 2). These findings demonstrate how solvation can fine-tune the photophysical properties of push–pull dyes, and this study highlights the importance of π-conjugated linkers in the excited state ICT process.