3,4-Ethylenedioxythiophene polymers

The conductivity of polymer 114 constituted by a Co(II)-salen-3,4-ethylenedioxythiophene polymer backbone has been shown to be sensitive when exposed to Lewis bases, such as pyridine and 2,6-lutidine [230]. This polymer was recently used as reversible chemoresistive sensor for nitric oxide (NO) [231] as well as catalyst for the reduction of O2 [232]. 

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. 

Lowering the Band Gap of Ethylenedioxythiophene Polymers Cyanovinylene-Linked Biheterocycles... 

Other thiophene-thiophene-5,5-dioxide copolymers were reported by Berlin et al. [544], who synthesized copolymers 443 and 444 with an alternating electron acceptor thiophene-5,5-dioxide unit and donor ethylenedioxythiophene (EDOT) units (Chart 2.107). The polymers absorbed at 535 nm (Eg = 2.3 eV) in chloroform solution and in films (which is consistent with their electrochemistry Eox 0.40-0.50 V, Emd -1.75-1.8 V AE 2.2-2.25 V) and emitted at 650 nm (<1> M (film) 1%). Such a high band gap (which exceeds that in PEDOT... 

M.P. de Jong, L.J. van Ijzendoorm, and M.J.A. de Voigt, Stability of the interface between indium-tin-oxide and poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) in polymer light-emitting diodes, Appl. Phys. Lett., 77 2255-2257, 2000. 

Fig. 1 Building units of conducting polymers, (1) polyacetylene (PA) (2) polypyrrole (PPy), polythiophene (PTh), polyfurane (PFu) (3) polyphenylene (PP) (4) polyaniline (PANI) 5 polyindole (PIND) (6) polycarbazole (PCaz) (7) polyazulene (Paz) (8) polynaphthalene (PNa) (9) polyanthracene (PAnth) (10) polypyrene (PPyr) (11) polyfluorene (PFiu) (12) poly(isothionaphthalene) (PITN) (13) poly(dithienothiophene) (14) poly(thienopyrrole) (15) poly(dithienylbenzene) (1G) poly(3-alkylthiophene) (17) poly(phenylene vinylene) (18) poly(bipyrrole) (PBPy), poly(bithiophene) (PBT) (19) poly(phenylenesulfide) (20) 4-poly(thienothiophene) (21) poly(thienyl vinylene), poly(furane vinylene) (22) poly(ethylenedioxythiophene) (PEDOT).

Baytron , a conducting polymer [154] derived from 3,4-ethylenedioxythiophene, is a commercially available product that can be used as an antistatic or electrostatic coating of plastics and glass. Moreover, it has successfully been applied as counterelectrode in capacitors and as a hole-injection layer in organic light-emitting diodes [155]. 

Scheme 4 Proposed stacking structure. The plane-to-plane distance d for the polymer shown in No. 19 is about 3.8 A [93-95], which is somewhat shorter than the d value (about 3.85 A) reported for head-to-tail-type poly(3-alkylthiophene) HT-P3RTh [128,129] and somewhat longer than the d values (3.6-3.65 A) observed with head-to-head-type poly(4-alkylthiazole-2,5-diyl) [124,129,130] and the charge-transfer-type copolymer of thiophene and 4-alkylthi-azole [131]. Poly(ethylenedioxythiophene) gives a similar d value (3.8 A) [132]. The existence of S in the aromatic ring seems to make the distance d longer...

Ghosh S, Rasmusson J, Inganaes O. Supramolecularself-assembly for enhanced conductivity in conjugated polymer blends. Ionic crosslinking in blends of poly(3,4-ethylenedioxythiophene)-poly(styiene sulfonate) and poly(vinylpyrrolidone). Adv Mater 1998 10 1097-1099. 

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... 

Sikora T, Marcilla R, Mecerreyes D, Rodriguez J, Pomposo JA, Ochoteco E (2009) Enzymatic synthesis of water-soluble conducting poly(3,4-ethylenedioxythiophene) a simple enzyme immobilization strategy for recycling and reusing. J Polym Sci A Polym Chem 47(l) 306-309... 

Polypyrrole was the first conducting polymer used as ion-to-electron transducer in solid-state ISEs [43], and is still one of the most frequently used [45-68]. Other conducting polymers that have been applied as ion-to-electron transducers in solid-state ISEs include poly(l-hexyl-3,4-dimethylpyrrole) [69,70], poly(3-octylthiophene) [44,70-74], poly(3,4-ethylenedioxythiophene) [75-86], poly(3-methylthiophene) [87], polyaniline [44,67,73,88-99], polyindole [100,101], poly(a-naphthylamine) [102], poly(o-anisidine) [67] and poly(o-aminophenol) [103], The monomer structures are shown in Fig. 4.1. 

The -conjugated polyselenophene named PEDOS (182) the analog of poly-3,4-ethylenedioxythiophene (PEDOT) [281], one of the most successful conductive polymers, was obtained from 3,4-ethylenedioxyselenophene (89) using different polymerization techniques. These were oxidative chemical polymerization, solid-state polymerization, transition metal-mediated polymerization, and electrochemical polymerization (Scheme 46) [293, 294], The derivatives of PEDOS having the... 

Kirchmeyer S, Reuter K, Simpson JC (2007) Poly(3,4-ethylenedioxythiophene) - scientific importance, remarkable properties, and applications. In Skotheim TA, Reynolds JR (eds) Handbook of conducting polymers. CRC, Boca Raton, chap 10, p 1... 

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. 

Rhenium(I) tricarbonyl-2,2 -bipyridine moieties were used to cap both ends of a poly fluorine, yielding Re-capped Re(bpy)(CO)3(py)-X-(py)(CO)3(bpy)Re 2+ polymers, where X = polyfluorene [51, 52], The polymers with and without the Re caps were spin-coated from their solutions in CH2C12 onto an ITO surface previously modified with a layer of poly(styrene sulfonic acid), doped with poly(ethylenedioxythiophene). The LED (light-emitting device) was then topped with a layer of Ca/Al. The photoluminescence (PL) and electroluminescence seen were consistent with the presence of [Re(bpy)(CO)3(py)]+ [158],... 

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