3.4- ethylenedioxythiophene synthesis

Bruno FF, Nagarajan R, Roy S, Kumar J, Samuelson LA (2003) Biomimetic synthesis of water soluble conductive polypyrrole and poly(3,4-ethylenedioxythiophene). J Macromol Sci A Pure Appl Chem A 40(12) 1327-1333... 

Rumbau V, Pomposo JA, Eleta A, Rodriguez J, Grande H, Mecerreyes D, Ochoteco E (2007) Eirst enzymatic synthesis of water-soluble conducting poly(3,4-ethylenedioxythiophene). Biomacromolecules 8(2) 315-317... 

Nagarajan R, Bruno FF, Samuelson LA, Kumar J (2004) Thiophene oligomer as a redox mediator for the biocatalytic synthesis of poly(3,4-ethylenedioxythiophene) [PEDOT]. Polym Prepr 45 195-196... 

Poly(3,4-ethylenedioxythiophene) (PEDOT) is a particularly popular conducting polymer as it can have good conductivity and stability and has a low band gap, which is pertinent to its use in photovoltaic devices. A number of authors have now studied the electrochemical synthesis of this polymer in different ionic liquids. Lu et al. [77] first demonstrated the use of [C4mim][BF4] to electrodeposit PEDOT onto ITO, and its application in an electrochromic numeric display. 

Aqueous colloidal dispersions created by template synthesis, principally used for processing polyaniline and poly(ethylenedioxythiophene), PEDOT. 

In a practical and simple synthesis of the valuable 3,4-ethylenedioxythiophene (EDOT) 7, 2,3-dimethoxy-l,3-butadiene 8 underwent transformation to 3,4-dimethoxythiophene 9 upon treatment with sulfur dichloride. Displacement of the methoxy groups with ethylene glycol in the presence of an acid catalyst finally gave the desired compound 7 <04TL6049>. 

A linear phthalocyanine containing polyesters 46 has been described [128,129], Recently, a linear polymeric phthalocyanine 47 prepared in a multistep synthesis with an iptycene architecture was briefly described [130]. At first two differently substituted l,3-dihydro-l,3-diiminoisoindolenines were statistically reacted. In the mixture of phthalocyanines obtained, the ethylenedioxythiophene part is introduced and the bis(ethyleneoxythiophene) oppositely substituted phthalocyanine was isolated by flash chromatography. Afterwards the thiophene parts in the phthalocyanine were electrochemically polymerized to obtain 47. 

Figure 10.20 SEM photograph of a single strand PPy-TBAPE6 (tetrabutylammonium-hexafluorophosphate) nanowire on a four-probe photolithography pattern. (Reprinted with permission from Synthetic Metals, Synthesis, characteristics, and field emission of doped and de-dopedpolypyrrole, polyaniline, poly(3,4-ethylenedioxythiophene) nanotubes and nanowires by B. H. Kim, D. H. Park, j. Joo et al., 150, 3, 279-284. Copyright (2005) Elsevier Ltd)...

S.I. Cho, R. Xiao, and S.B. Lee, Electrochemical synthesis of poly(3,4-ethylenedioxythiophene) nanotubes towards fast window-type electrochromic devices. Nanotechnology 18, 405705 (2007). 

M.A. Khan and S.P. Armes, Synthesis and characterization of micrometer-sized poly(3,4 ethylenedioxythiophene)-coated polystyrene latexes, Langmuir, 15(10), 3469 3475 (1999). 

Liu, R., Duay, J., Lee, S.B., 201 lb. Electrochemical formation mechanism for the controlled synthesis of heterogeneous Mn02/poly(3,4-ethylenedioxythiophene) nanowires. ACS Nano 5,5608-5619. 

K. Singh, A. Ohlan, P. Saini, S. K. Dhawan, Poly (3,4-Ethylenedioxythiophene) y-Fe203 Polymer Composite-Super Paramagnetic Behavior and Variable Range Hopping ID Conduction Mechanism-Synthesis and Characterization. Polym Adv Technol 2008,19, 229-236. 

The synthesis of poly(3,4-ethylenedioxythiophene (PEDOT) derivatives can be classified into three different types of polymerization reactions ... 

Synthesis of Poly(3,4-Ethylenedioxythiophene) in a Poly(Vinyl Acetate) Matrix... 

Caras-Quintero, D., and P. Bauerle. 2004. Synthesis of the first enantiomerically pure and chiral, disubstituted 3,4-ethylenedioxythiophenes (EDOTs) and corresponding stereo- and regioregular PEDOTs. Chem Commun 8 926-927. 

Lefebvre, M., Z.G. Qi, D. Rana, and P.G. Pickup. 1999. Chemical synthesis, characterization, and electrochemical studies of poly(3,4-ethylenedioxythiophene)/poly(styrene-4-sulfonate) composites. Chem Mater 11 (2) 262-268. 

Early progress in polythiophene chemistry was achieved by the synthesis of mono- and dialkoxy-substituted thiophene derivatives developed by Leclerc [6] and industrial scientists at Hoechst AG [7-9]. However, most polymers of mono- and dialkoxythiophenes exhibited low conductivity in the oxidized, doped state. A breakthrough in this area was the synthesis of polymers of the bicyclic 3,4-ethylenedioxythiophene (EDT or EDOT) and its derivatives—electrochemically polymerized by Heinze et al. and chemically polymerized by Jonas et al. of the Bayer Corporate Research Laboratories [10,11]. In contrast to the nonbicyclic polymers of mono- and dialkoxythiophenes, PEDT has a very stable and highly conductive cationic doped state. The low HOMO-LUMO bandgap of conductive PEDT allowed the formation of a tremendously stable, highly conductive ICP [12]. Technical use and commercialization quickly followed today ICPs based on PEDT are commercially available in multiton quantities. 

Thomas, C.A. and J.R. Reynolds. 1999. Lowering the band gap of ethylenedioxythiophene polymers Cyanovinylene-linked biheterocycles. Semiconducting polymers Applications, properties, and Synthesis, eds. B.R. Hsieh and Y. Wei. Vol. 735. Washington DC American Chemical Society, p. 367. 

Zotti, G., S. Zecchin, G. Schiavon, and L. Groenendaal. 2002. Electrochemical and chemical synthesis and characterization of sulfonated poly(3,4-ethylenedioxythiophene) A novel water-soluble and highly conductive conjugated oligomer. Macromol Chem Phys 203 1958-1964. 

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