Hongmei Du

Soluble Electrochromic Polymers Incorporating Benzoselenadiazole and Electron Donor Units (Carbazole or Fluorene): Synthesis and Electronic-Optical Properties

A series of π-conjugated polymers containing alternating benzoselenadiazole (BSe)-bi(thiophene derivative)-carbazole or benzoththiadiazole (BSe)-bi(thiophene derivative)-fluorene units were designed and synthesized. Thiophene derivatives, namely 3-hexylthiophene, 3,4-bihexyloxythiophene, and 3,4-bioctyloxythiophene, were used as the π-bridges of the polymers. The polymers were characterized in detail in terms of their thermal stabilities, cyclic voltammograms, UV-Vis absorption, spectroelectrochemistry, dynamic switching property and so forth. The alkoxy thiophene π-bridged polymers have lower onset oxidation potentials and bandgaps than that of their corresponding alkyl thiophene π-bridged polymers. The selection of the donor units between the carbazole and the fluorene units has nearly no effect on the bandgaps and colors as well as the onset oxidation potentials of the polymers. The increase in the length of the side alkyl chains on the thiophene ring caused a slight increase in the polymer bandgap, which may be caused by the space hindrance effect. The dynamic switching abilities of the polymers were obtained by the chronoabsorptometry method, and the results also suggested that the alkoxy thiophene-containing polymers (as π-bridges) have higher contrast ratios than the corresponding alkyl thiophene-containing polymers. Furthermore, the increase in the length of the side alkyl chain might have a detrimental effect on the optical contrast ratios of the polymers.

Synthesis and characterization of novel donor–acceptor type neutral green electrochromic polymers containing an indolo[3,2-b]carbazole donor and diketopyrrolopyrrole acceptor

Indolocarbazole bearing donor–acceptor type polymers have rarely been reported in the electrochromic field despite them having considerable development in the applications of organic photoelectric devices. In this paper, two novel soluble electrochromic polymers, namely PDTCZ-1 and PDTCZ-2, were prepared by chemical polymerization including indolo[3,2-b]carbazole (IC) units as the donor, diketopyrrolopyrrole (DPP) units as the acceptor and bithiophene units as the bridging group. Through diverse characterization techniques such as cyclic voltammetry (CV), scanning electron microscopy (SEM), UV-vis spectroscopy and thermogravimetric analysis (TGA), it was found that PDTCZ-1 and PDTCZ-2 exhibited saturated green in the neutral state and pale green in the oxidized state with optical band gaps of 1.44 eV and 1.39 eV, respectively, as well as demonstrating fast switching speed, satisfactory coloration efficiency and favorable thermal stability. In addition, the proportion of donors to acceptors definitely exerted an influence on the electrochromic properties of the polymers. As the thiophene/IC/DPP ratio changed from 4/3/1 (PDTCZ-1) to 5/4/1 (PDTCZ-2), meaning an increase of the donor ratio, the polymer showed a reduced onset oxidation potential, decreased optical band gap and different dynamic parameters. The positive results suggest that PDTCZ-1 and PDTCZ-2 could be promising candidates as neutral green electrochromic materials and deserve more attention and penetrating research.

Synthesis and characterization of novel donor–acceptor type electrochromic polymers containing diketopyrrolopyrrole as an acceptor and propylenedioxythiophene or indacenodithiophene as a donor

A range of low band gap donor–acceptor conjugated polymers (P1–P3) with backbones composed of diketopyrrolopyrrole (DPP), propylenedioxythiophene (ProDOT) and indacenodithiophene (IDT) units were designed and synthesized using the Stille coupling reaction. The optical, electrochemical and electrochromic properties of the resultant polymers were thoroughly characterized. These polymers showed exceptional solubility in common organic solvents and displayed thermal stability at a high temperature. The optical and electrochemical measurements revealed slight variations in the maximum absorptions and oxidation peaks depending on the intrinsic D–A ratio in each polymer, and narrow band gaps lower than 1.60 eV were found for these polymers. Upon oxidation, the polymer films exhibit distinct color changes (pale violet-red to dark gray for P1, rosy brown to silver for P2, atrovirens to light grey for P3) in the VIS and NIR regions. Moreover, the electrochromic switching studies indicated that these polymers have favorable switching properties, such as rapid response speed and high optical contrast and coloration efficiency, and are outstanding candidates for electrochromic applications.

Effects of Pyrazine Derivatives and Substituted Positions on the Photoelectric Properties and Electromemory Performance of D–A–D Series Compounds

Pyrazine derivatives quinoxaline and pyridopyrazine were selected as the acceptors, and benzocarbazole was used as the donor to synthesize four different D–A–D compounds. The results showed that 2,3-bis(decyloxy)pyridine[3,4-b]pyrazine (DPP) exhibited stronger electron-withdrawing ability than that of 2,3-bis(decyloxy)quinoxaline (DPx), because DPP possesses one more nitrogen (N) atom, resulting in a red-shift of the intramolecular charge transfer (ICT) absorption bands and fluorescent emission spectra for compounds with DPP as the acceptor compared with those that use DPx as the acceptor. The band-gap energy (Eg) of the four D–A–D compounds were 2.82 eV, 2.70 eV, 2.48 eV, and 2.62 eV, respectively, for BPC-2DPx, BPC-3DPx, BPC-2DPP, and BPC-3DPP. The solvatochromic effect was insignificant when the four compounds were in the ground state, which became significant in an excited state. With increasing solvent polarity, a 30–43 nm red shift was observed in the emissive spectra of the compounds. The thermal decomposition temperatures of the four compounds between 436 and 453 °C had very high thermal stability. Resistor-type memory devices based on BPC-2DPx and BPC-2DPP were fabricated in a simple sandwich configuration, Al/BPC-2DPx/ITO or Al/BPC-2DPP/ITO. The two devices showed a binary non-volatile flash memory, with lower threshold voltages and better repeatability.