In this paper, we study three symmetrical D-π-D chromophores containing dithieno[3,2-b:2′,3′-d]thiophene (DTT) as the π-center and various donor end moieties, by means of UV-vis-NIR and FT-Raman spectroscopy and in situ spectroelectrochemistry. The compounds display dual redox properties: all exhibited two oxidations and single stable reduction peaks contrarily to the one or two oxidations and none reduction which could be anticipated in view of their chemical structures. We analyze the possible electronic modulation by the π-conjugated DTT relay in the redox process and electronic coupling between the two electron donor (D) units attached through conjugation to opposite sides of the π-linker. To this end, the UV-vis-NIR and FT-Raman spectra of the neutral compounds and of the charged species generated upon in situ p- or n-doping have been recorded and interpreted with the help of Density Functional Theory (DFT) calculations. The analysis of the peculiar Raman features of these π-conjugated chromophores is guided by the formalism of the Effective Conjugation Coordinate (ECC) theory. This research shows that the Raman spectroscopic characterization of this type of D-π-D structures is a powerful tool to derive information about their π-conjugational properties in the pristine and doped states.
ASJC Scopus subject areas
- Colloid and Surface Chemistry