The impact of structural modification on the electrochromic and electroluminescent properties of D–A–D benzothiadiazole derivatives with a fluorene linker and (Bi)thiophene units†

Abstract

Two donor–acceptor–donor (D–A–D) derivatives of benzothiadiazole (BTD) symmetrically functionalized with dihexylfluorene units serving as a linker between the BTD core and the thiophene (Th-FBTD) or bithiophene (2Th-FBTD) electron-donating groups were designed, synthesized and comprehensively characterized. Both compounds show high photoluminescence quantum yield (PLQY) both in solution and in the solid state. Th-FBTD demonstrates PLQY values of 82% and 96%, whereas 2Th-FBTD exhibits values of 74% and 97% in DCM and Zeonex, respectively. These compounds were employed as emissive dopants in multilayer solution-processed OLEDs, resulting in green electroluminescence with an emission peak at ca. 540 nm. The OLEDs display comparable performance, with a maximum external quantum efficiency of 3.5% for Th-FBTD and 2.8% for 2Th-FBTD. Both Th-FBTD and 2Th-FBTD undergo quasi-reversible electrochemical reduction and irreversible oxidation, giving stable electroactive polymer layers of bipolar character: p(Th-FBTD) and p(2Th-FBTD). The electrodeposited polymers undergo one-step reversible reduction and two-step reversible oxidation. Their electrochemical oxidation is accompanied by a reversible color change. Analysis of the optical density difference and coloration efficiency revealed improved electrochromic properties in both visible and near-infrared (NIR) ranges in p(2Th-FBTD) compared to that in p(Th-FBTD).