Mechanistic studies of the electropolymerization of 2,2′-bithiophene and of pyrrole to form conducting polymers

Funt, B. Lionel; Lowen, Stephen V.

doi:10.1016/0379-6779(85)90059-1

Cited by 54 publications

(16 citation statements)

References 16 publications

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“…Peak I, around 0.68 V, was assigned to p-doping of the as-prepared polymer chains, which appeared from the second sweep onwards. The two reduction peaks (0.65 V and 0.25 V) were assigned to two stable states of partially discharged polymer chains [36]. The generated polymer (polybithiophene) was of high stability as the charging and discharging processes were fully reversible.…”

Section: Resultsmentioning

confidence: 99%

Thin Functional Polymer Films by Electropolymerization

et al. 2019

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Intrinsically conducting polymers (ICPs) have been widely utilized in organic electronics, actuators, electrochromic devices, and sensors. Many potential applications demand the formation of thin polymer films, which can be generated by electrochemical polymerization. Electrochemical methods are quite powerful and versatile and can be utilized for investigation of ICPs, both for educational purposes and materials chemistry research. In this study, we show that potentiodynamic and potentiostatic techniques can be utilized for generating and characterizing thin polymer films under the context of educational chemistry research and state-of-the-art polymer research. First, two well-known bifunctional monomers (with only two linking sites)—aniline and bithiophene—and their respective ICPs—polyaniline (PANI) and polybithiophene (PBTh)—were electrochemically generated and characterized. Tests with simple electrochromic devices based on PANI and PBTh were carried out at different doping levels, where changes in the UV-VIS absorption spectra and color were ascribed to changes in the polymer structures. These experiments may attract students’ interest in the electrochemical polymerization of ICPs as doping/dedoping processes can be easily understood from observable color changes to the naked eye, as shown for the two polymers. Second, two new carbazole-based multifunctional monomers (with three or more linking sites)—tris(4-(carbazol-9-yl)phenyl)silanol (TPTCzSiOH) and tris(3,5-di(carbazol-9-yl)phenyl)silanol (TPHxCzSiOH)—were synthesized to produce thin films of cross-linked polymer networks by electropolymerization. These thin polymer films were characterized by electrochemical quartz crystal microbalance (EQCM) experiments and nitrogen sorption, and the results showed a microporous nature with high specific surface areas up to 930 m2g−1. PTPHxCzSiOH-modified glassy carbon electrodes showed an enhanced electrochemical response to nitrobenzene as prototypical nitroaromatic compound compared to unmodified glassy carbon electrodes.

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Section: Resultsmentioning

confidence: 99%

Thin Functional Polymer Films by Electropolymerization

et al. 2019

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“…Published data for P(DTT) P1 is very similar showing an onset potential of −0.12 V vs Fc/Fc + (calculated from 0.37 V vs Ag/AgCl) [46,52]. The redox characteristic of P1–P4 is slightly more negative compared to the non-bridged counterparts, namely poly(bithiophene) [48–50] and poly(biselenophene) [51] (both show E onset at ca. −0.0 V vs Fc/Fc + ) indicating that the chalcogenide bridges do not much influence the electrochemical properties of the corresponding conjugated polymers.…”

Section: Xrd Powder Measurementsmentioning

confidence: 97%

“…Because of the structural similarity of heterotriacenes 1 – 4 to 2,2’-bithiophene and 2,2’-biselenophene, which can be oxidatively polymerized to polythiophenes [48–50] or polyselenophenes [51], respectively, we were interested in the electropolymerization of heterotriacenes 1 – 4 to the corresponding conjugated polymers P1–P4 . Hence, monomers 1 – 4 were subjected to potentiodynamic polymerization in dichloromethane/TBAPF 6 as electrolyte and the redox and optical properties of the obtained films were determined.…”

Section: Xrd Powder Measurementsmentioning

confidence: 99%

Selenophene-containing heterotriacenes by a C–Se coupling/cyclization reaction

Schwartz

Förtsch

Vogt

et al. 2019

Beilstein J. Org. Chem.

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A new novel family of tricyclic sulfur and/or selenium-containing heterotriacenes 2–4 with an increasing number of selenium (Se) atoms is presented. The heterotriacene derivatives were synthesized in multistep synthetic routes and the crucial cyclization steps to the stable and soluble fused systems were achieved by copper-catalyzed C–S and C–Se coupling/cyclization reactions. Structures and packing motifs in the solid state were elucidated by single crystal X-ray analysis and XRD powder measurements. Comparison of the optoelectronic properties provides interesting structure–property relationships and gives valuable insights into the role of heteroatoms within the series of the heterotriacenes. Electrooxidative polymerization led to the corresponding poly(heterotriacene)s P2–P4.

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“…Preparation of polymer films by oxidation and electropolymerization of aromatic compounds (aniline, phenol, benzene, and their derivatives) 1–6 and of heteroaromatic compounds (pyrrol, tiophene, and their derivatives) 7–11 has been widely used in electrode surface modification as a mean to obtain interesting electrode properties. The increasing development of new electrode materials has motivated the electropolymerization study of new organic molecules.…”

Section: Introductionmentioning

confidence: 99%

“…The increasing development of new electrode materials has motivated the electropolymerization study of new organic molecules. Most studies have been devoted to improvement of the electropolymerization conditions and properties 12 of the polymer films, although attempts have been made to envisage oxidation and electropolymerization mechanisms using cyclic voltammetry 1, 8, 9, 13–15, spectroscopic techniques 1, 13, and theoretical calculations 7, 16–23.…”

Section: Introductionmentioning

confidence: 99%

Prediction of reactive sites for the electropolymerization of p‐benzenesulfonic acid derivatives: Ab initio and experimental study

Nabais

Fartaria

Fernandes

et al. 2004

Int J of Quantum Chemistry

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ABSTRACT:A theoretical study of the electronic structure of some p-benzenesulfonic acid derivatives is carried out to explain the electrooxidation of these compounds, in particular the allyl ether p-benzenesulfonic acid, sodium salt electrooxidation, and electrode surface modification observed during electrochemical studies. The effects of the alkyl side chain and of the aromatic ring during electrooxidation are considered using the UHF and B3LYP levels of theory. The changes in monomer structure after removal of an electron are explained by the nodal structure of the highest occupied molecular orbital (HOMO), ␣ and ␤ single occupied molecular orbitals (SOMO) and by their energies. Apart from frontier molecular orbital theory, charge reaction control, which is expected to occur at higher oxidation potentials, is also discussed. The calculations indicate that the unpaired electron spin distribution and atomic charge variation in the radical cation is very sensitive to the nature of the alkyl side chain. In fact, this distribution reflects the electronic structure of these monomers related to their oxidability. It is shown that the removal of an electron is carried out by two competing mechanisms.

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Mechanistic studies of the electropolymerization of 2,2′-bithiophene and of pyrrole to form conducting polymers

Cited by 54 publications

References 16 publications

Thin Functional Polymer Films by Electropolymerization

Thin Functional Polymer Films by Electropolymerization

Selenophene-containing heterotriacenes by a C–Se coupling/cyclization reaction

Prediction of reactive sites for the electropolymerization of p‐benzenesulfonic acid derivatives: Ab initio and experimental study

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