Poly[trans-bis(3,4-ethylenedioxythiophene)vinylene]: a low band-gap polymer with rapid redox switching capabilities between conducting transmissive and insulating absorptive states

Sotzing, Gregory A.; Reynolds, John R.

doi:10.1039/c39950000703

Cited by 54 publications

(27 citation statements)

References 6 publications

(4 reference statements)

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“…Extrapolation to 1/Cn ‫ס‬ 0 gives a DE of 1.41 eV for an infinite poly(thienylenevinylene) with alkoxy groups. This value is in good agreement with those reported for the bandgap of poly(thienylenevinylene) with alkoxy groups (1.2-1.4 eV) [20][21][22].…”

supporting

confidence: 91%

“…Alkoxy derivatives have several advantages over the alkyl-substituted ones since alkoxy groups are more effective to raise the HOMO energy level than alkyl groups; the presence of alkoxy groups in place of alkyl substituents decreases the ionization potential of polymers and oligomers. Thus, if the oxygen is directly attached to the ring, the band gap (DE) of poly(thio- phenes) [20] or poly(thienylenevinylenes) [21][22] can be reduced by a substantial amount and the conducting states of the polymer are stabilized. Polythiophenes fused with pyrazine and ethylenedioxy rings in an alternate way have an extremely narrow bandgap (0.36 eV) [23].…”

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confidence: 99%

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Synthesis of oligo(thienylenevinylenes) substituted with alkoxy groups

Ono

Okumura

Mutoh

2001

Heteroatom Chemistry

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Conjugated oligomers based on a combination of thiophene and 3,4-dialkoxythiophene moieties have been synthesized via the Vilsmeier formylation, Wittig-Honer reaction, and McMurry coupling reaction starting from dimethyl 3,4-dihydroxythioLinear p-conjugated molecular or polymeric systems are the focus of extensive current research interest for their opt-electronic properties and their potential applications in the field of opt-electronic devices, such as light-emitting diodes [1], field effect transistors [2,3], and nonlinear optics (NLO) [4,5]. More recently, their potential use as molecular wires in molecular electronics has attracted much attention [6]. Oligo(thiophenes) [7,8], oligo(thienylenevinylenes) [9][10][11][12], oligo(phenylenevinylene) [13][14][15][16] other related oligomers [17] possessing well-defined conjugated lengths and oligomers [17] possessing well-defined conjugated lengths and structures have been prepared in order to contribute to a better understanding of electronic materials. Roncali and his coworkers constructed extended thienylenevinylene oligomers using 3,4-dihexylthiophene as a building block and found that oligo(thienylenevinylenes) are the most efficient extended molecular wires among the known p-conjugated systems [9][10][11][12]. Long alkyl groups such as the hexyl group are required to improve the solubility of the higher oligomers and also serve as electron-donating groups to control the electronic properties of p-conjugated systems. In this article, we report a new type of oligo(thienylenevinylenes) consisted of a mixture of 3,4-dialkoxythiophene and thiophene rings. Since 3,4-dialkoxythiophenes are more electron rich than unsubstituted thiophenes, oligomers linked with such thiophene units are expected to show a narrow highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy gap. Furthermore, S • • • O intramolecular interaction may contribute to reduce the HOMO-LUMO energy gap. Fine tuning of the HOMO and LUMO energies of molecular wires is essential for efficient electron transport over a long distance [18,19]. Alkoxy derivatives have several advantages over the alkyl-substituted ones since alkoxy groups are more effective to raise the HOMO energy level than alkyl groups; the presence of alkoxy groups in place of alkyl substituents decreases the ionization potential of polymers and oligomers. Thus, if the oxygen is directly attached to the ring, the band gap (DE) of poly(thio-

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supporting

confidence: 91%

mentioning

confidence: 99%

Synthesis of oligo(thienylenevinylenes) substituted with alkoxy groups

Ono

Okumura

Mutoh

2001

Heteroatom Chemistry

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“…Alkoxy-substituted polythiophenes are currently being intensively investigated for their electrochromic properties (27)(28)(29)(30)(31)(32)(33)(34). Materials based on poly(3,4-(ethylenedioxy)thiophene) (PEDOT) have a band gap lower than polythiophene and alkyl-substituted polythiophenes, owing to the presence of the two electrondonating oxygen atoms adjacent to the thiophene unit.…”

Section: R = C 7 H 15mentioning

confidence: 99%

Chromogenic Materials, Electrochromic

Samat

Guglielmetti

2004

Kirk-Othmer Encyclopedia of Chemical Technology

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Electrochromism is a reversible color change in a material, often a thin film, that accompanies an oxidation–reduction reaction driven by a small current at low voltage. It occurs at or near room temperature in both cathodically colored and anodically colored inorganic and organic compounds. It is accompanied by ion insertion/extraction (doping/undoping) for charge balance in thin solid films. Electrochromic chromogenic materials are divided into two groups based on whether or not insertion/extraction occurs or does. For the smaller, noninsertion group , reversible coloration occurs in solution or is associated with reversible electrodeposition from solution. The best known members are viologens, polymers systems such as polyheterocycles, metallopolymers, metal phthalocyanines, and inorganic electrodeposition of silver halides. In the insertion/extraction group, three main categories of systems have been investigated: Cathodically colored inorganic materials usually color with either H + or alkali ion insertion. The best known film is amorphous tungsten oxide, in part, because of its relatively high coloration efficiency in the visible region. Anodically colored inorganic materials, including Prussian blue, also having a high coloration efficiency, and hydrated oxides of iridium and nickel. Often, K + is inserted for Prussian blue. There is a lively debate about whether H + or OH − is active for the hydrated oxides. Doped/undoped organic films color both anodically and cathodically in general. There is much less known about this type of electrochromism in literature which, as a whole, has been reviewed through 1990. Polyaniline, polypyrrole, polythiophene or tetrathiafulvalene systems with dopants as proton, alkaline metal or ClO 4 − , BF 4 − anions have been studied. A recent system concerns the preparation of electrochromic layers by using sol–gels formation controlling the variation of the viscosity of the electrolyte and polymer. Many potential applications are possible but some technical aspects have yet to be improved for a commercial availability.

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“…10 Horner-Wadsworth-Emmons (HWE) reaction between 3 and 3,4-ethylenedioxythiophenecarbaldehyde, yielded trans-bis-(3,4-ethylene-dioxythiophene)-vinylene (4) as a yellow solid in 88% yield, showing that to be a better procedure than the method previously described (49%) from a Grignard reagent. 11 Double Vilsmeier formylation reaction of 4 afforded bisaldehyde 5, in quantitative yield. The crucial step was the HWE olefination between the corresponding phosphonate-Zn-porphyrin 12 and 4 under careful stoichiometry control giving monoaldehyde 6 in 42% yield as a red solid (mp >300°C), purified by column chromatography (silica gel, hexane:dichloromethane, 3:7).…”

Section: Introductionmentioning

confidence: 99%