Solution-Processable Copolymers Based on Triphenylamine and 3,4-Ethylenedioxythiophene: Facile Synthesis and Multielectrochromism.

In comparison with traditional inorganic electrochromic materials, organic polymers offer advantages such as fast switching speed, flexibility, lightweightness, low cost and nontoxicity, solution-processability, and color tunability. Herein, a series of hyper-branched copolymers are synthesized from triphenylamine and 3,4-ethylenedioxythiophene with different feed ratios via iron(III) chloride (FeCl3 )-mediated oxidative polymerization. The resultant organic-soluble polymers are easily processable and their corresponding electrochromic devices are found to be stable with limited degradation upon 2500 cycles. In addition to their facile synthesis to achieve solution-processable polymers, studies also show that the polymers exhibit multielectrochromic properties and give rise to five colored states upon oxidative-doping by applying an external voltage between 0 and 2.0 V, providing an interesting example of polymers with unique electrochromic switching among up to five colors, from yellow at the neutral state, to pale green, pale purple, orange, and finally gray.

Cyclization of Tetraaryl-Substituted Benzoquinones and Hydroquinones through the Scholl Reaction.

2,3,5,6-Tetrakis(5'-dodecylthiophen-2-yl)-benzoquinones and 2,3,5,6-tetrakis(5'-dodecylthiophen-2'-yl)-hydroquinones were prepared via the Stille or Suzuki cross-coupling reactions, followed by oxidation by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in the case that aryl groups are dodecylthiophenyl. 2,3,5,6-Tetrakis(5'-dodecylthiophen-2'-yl)benzoquinone and 2,3,5,6-tetrakis(5'-dodecylthiophen-2'-yl)-1,4-bis(dodecyloxy)benzene underwent the Scholl reaction to give their corresponding predictable cyclization products anthra[2,1-b:3,4-b':6,5-b″:7,8-b‴]tetrathiophene-7,14-dione (3) and anthra[1,2-b:4,3-b':5,6-b″:8,7-b‴]tetrathiophene (5), respectively. Cyclization of 2,3,4,5-tetra(p-tert-butyl-phenyl) benzoquinones through the Scholl reaction, however, gave rise to a mixture of two cyclization products including an unusual major product, benzo[4',5']furo[3',2':3,4]triphenyleno[1,2-b]benzofuran (9), with 84% yield and a minor product, 2,3-diphenyltriphenylene-1,4-diol (10), with 11% yield. In contrast, cyclization of 2,3,4,5-tetrakis(p-dodecyloxyphenyl)benzoquinone only afforded 2,3-diphenyltriphenylene-1,4-diol (8) with 34% yield. The optical and electrochemistry properties of these fused aromatics were studied. Light emitting diode devices using compound 9 as the fluorescent dopant were fabricated. A maximum external quantum efficiency of 3.23% was achieved for a 4,4'-bis(carbazole)biphenyl/9 based device, revealing the potential for such fused aromatics as dopant to be a blue LED component, subject to the functionalization on these novel π-structures as well as further device optimization.

Effects of Chemical Composition, Film Thickness, and Morphology on the Electrochromic Properties of Donor-Acceptor Conjugated Copolymers Based on Diketopyrrolopyrrole.

A series of diketopyrrolopyrrole (DPP) and propylenedioxythiophene (ProDOT)-containing random copolymers with different donor-to-acceptor ratios is synthesized through Stille coupling polymerizations. The low-bandgap polymers display dark tones with colors ranging from magenta to blue, and reveal reversible colored-to-transmissive electrochromism in absorption/transmission-type devices with high optical contrasts (up to 48 and 77 % in the visible and near-infrared regions, respectively), modest switching speeds (a few to tens of seconds) and coloration efficiencies (267-574 cm2 C-1 ), as well as good long-term ambient redox stabilities. The structure-performance relationship of the polymers, in particular, the role of donor-to-acceptor ratio, is investigated, and it is shown that an increase in the amount of acceptor in the polymers leads to slower oxidative but faster reductive switching, accompanied with enhancement of the redox stability. In addition, further study on the influence of film thickness and film morphology reveals that devices with higher optical contrasts are attainable from thicker polymer films at the expense of switching speeds; films with high uniformity and connectedness together with open, loose structures at submicron to micron scale are favorable for achieving good electrochromic performance.

Dithienothiophene-Based Triphenylamine-Containing Branched Copolymers for Electrochromic Applications.

A series of dithienothiophene-based electrochromic polymers are synthesized by a Stille coupling reaction of 2,6-bis(trimethylstannyl)dithieno[3,2-b:2',3'-d]thiophene, 2,5-dibromo-3,4-bis(dodecyloxy)thiophene, and tris(4-bromophenylamine). The resulting polymers have high molecular weights in the range of 59 200 to 81 300 g mol-1 , and good solubility in common organic solvents. The polymer films are purple/red in neutral states and gradually become gray when oxidized to an intermediate state and blue when fully oxidized. Incorporation of triphenylamine into the polymer chains has resulted in a significant increase in the redox stability, which renders this a potential method to create high-performance electrochromic polymers.

Electrospun aggregation-induced emission active POSS-based porous copolymer films for detection of explosives.

Electrospun aggregation-induced emission (AIE)-active polyhedral oligomeric silsesquioxane (POSS)-based copolymer films exhibit an approximately 9-fold increase in response to explosive vapors compared to dense films although porous copolymer films have a thickness as high as 560 ± 60 nm.

Synthesis of ultrahighly electron-deficient pyrrolo[3,4-d]pyridazine-5,7-dione by inverse electron demand Diels-Alder reaction and its application as electrochromic materials.

A new electron acceptor 6-alkylpyrrolo[3,4-d]pyridazine-5,7-dione (PPD) with a very low LUMO level has been synthesized via a challenging inverse electron demand Diels-Alder reaction between thiophene and furan-decorated tetrazine substrates and an electron-deficient 1-alkyl-1H-pyrrole-2,5-dione unit. The PPD monomer has been incorporated into a series of donor-acceptor-type conjugated polymers as electrochromic materials with good optical contrast, fast switching speed, and high coloration efficiency.