In situ EPR spectroelectrochemical studies of paramagnetic centres in poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-butylenedioxythiophene) (PBuDOT) films

Zykwinska, Agata; Domagała, Wojciech; Czardybon, A.; Pilawa, Barbara; Łapkowski, Mieczysław

doi:10.1016/s0301-0104(03)00253-2

Cited by 64 publications

(41 citation statements)

References 20 publications

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“…This conclusion is in good agreement with the high spin [ 17,55,56 ] and charged state [ 57 ] content detected in reduced fi lms of conducting polymers by electron paramagnetic resonance (EPR) or Raman spectroscopy. Beyond the closing potential, both electronic and ionic fi lm conductivities must be high enough to allow the electrochemical reduction to go beyond -2.50 V. Most of the available analytical methodologies allow the detection of such high ionic concentrations in the fi lm.…”

Section: The Proton's Infl Uencesupporting

confidence: 87%

Structural Electrochemistry from Freestanding Polypyrrole Films: Full Hydrogen Inhibition from Aqueous Solutions

Otero

Martínez

Fuchiwaki

et al. 2013

Adv Funct Materials

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Free-standing polypyrrole fi lms, being the metal-polymer contact located several millimeters outside the electrolyte, give stationary closed coulovoltammetric (charge/potential) loop responses to consecutive potential sweeps from -2.50 V to 0.65 V in aqueous solutions. The continuous and closed charge evolution corroborates the presence of reversible fi lm reactions (electroactivity), together high electronic and ionic conductivities in the full potential range. The closed charge loop demonstrates that the irreversible hydrogen evolution is fully inhibited from aqueous solutions of different salts up to -2.5 V vs Ag/AgCl. The morphology of the closed charge loops shows abrupt slope changes corresponding to the four basic components of the structural electrochemistry for a 3D electroactive gel: reduction-shrinking, reduction-compaction, oxidation-relaxation, and oxidation-swelling. Freestanding fi lms of conducting polymers behave as 3D gel electrodes (reactors) at the chain level, where reversible electrochemical reactions drive structural conformational and macroscopic (volume variation) changes. Very slow hydrogen evolution is revealed by coulovoltammetric responses at more cathodic potentials than -1.1 V from strong acid solutions, or in neutral salts self-supported blend fi lms of polypyrrole with large organic acids. Conducting polymers overcome graphite, mercury, lead, diamond, or carbon electrodes as hydrogen inhibitors, and can compete with them for some electro-analytical and electrochemical applications in aqueous solutions.

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Section: The Proton's Infl Uencesupporting

confidence: 87%

Structural Electrochemistry from Freestanding Polypyrrole Films: Full Hydrogen Inhibition from Aqueous Solutions

Otero

Martínez

Fuchiwaki

et al. 2013

Adv Funct Materials

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“…The different rate between both transfers can be caused by the formation of two kinds of charge defects (polarons) previously observed in PEDOT [61] and derivative polymers [62,63]. On the one hand, the faster free water transfer can be related to highly mobile polarons delocalized on isolated polymer segments involving fast conformational movements of PEDOT backbone.…”

Section: 1mentioning

confidence: 93%

Electrochemically induced free solvent transfer in thin poly(3,4-ethylenedioxythiophene) films

Agrisuelas

Gabrielli

Garcı́a-Jareño

et al. 2015

Electrochimica Acta

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“…[73][74][75][76] Moreover polarons carry unpaired spins, thus their formation and recombination to bipolarons can be monitored by EPR spectroscopy. [77][78][79][80] Spectroscopic parameters of the investigated polymers in the neutral and p-doped states are collected in Table 9. With the exception of poly (4), in the spectra of thin films of neutral polymers a clear vibrational structure can be seen, which is the most pronounced in poly(3).…”

Section: Uv-vis-nir and Epr Spectroelectrochemistry Of The Electropolmentioning

confidence: 99%

Symmetrically Disubstituted Bithiophene Derivatives of 1,3,4-Oxadiazole, 1,3,4-Thiadiazole, and 1,2,4-Triazole – Spectroscopic, Electrochemical, and Spectroelectrochemical Properties

et al. 2014

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Electrochemical and spectroelectrochemical properties of a series of new penta-ring donor -acceptor compounds, comprising 1,3,4-oxadiazole, 1,3,4-thiadiazole and 1,2,4-triazole central ring, symmetrically connected to substituted bithiophenes, were investigated. Aromaticity and electrophilic -nucleophilic traits of the aza-heterocyclic units, fostering inductive and resonance effects that translate to conjugation enhancement and electron (de)localization, were found a major factor determining the key electron properties of ionization potential (IP) and electron affinity (EA) of these molecules. Replacing the alkyl thiophene substituent for an alkoxy one, afforded certain control over the two parameters as well. All studied compounds were found to undergo electrochemical polymerization giving p and n-dopable products, featuring good electrochemical reversibility of their oxidative doping process, as demonstrated by cyclic voltammetry and UV-Vis-NIR, EPR spectroelectrochemistry. While electropolymerisation of entities differing in the heterodiazole unit was found to conserve the EA value, the IP parameter of polymerisation products was found to decrease by 0.6 to 0.7 eV affording an asymmetric narrowing of the frontier energy levels gap. Aided by quantum chemical computations, the effects of structure tailoring of the investigated systems are rationalized, pointing to conscious ways of shaping the electronic properties of thiophene class polymers using synthetically convenient heterodiazole π-conjugated units.

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In situ EPR spectroelectrochemical studies of paramagnetic centres in poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-butylenedioxythiophene) (PBuDOT) films

Cited by 64 publications

References 20 publications

Structural Electrochemistry from Freestanding Polypyrrole Films: Full Hydrogen Inhibition from Aqueous Solutions

Structural Electrochemistry from Freestanding Polypyrrole Films: Full Hydrogen Inhibition from Aqueous Solutions

Electrochemically induced free solvent transfer in thin poly(3,4-ethylenedioxythiophene) films

Symmetrically Disubstituted Bithiophene Derivatives of 1,3,4-Oxadiazole, 1,3,4-Thiadiazole, and 1,2,4-Triazole – Spectroscopic, Electrochemical, and Spectroelectrochemical Properties

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