Electrodeposition and properties of TEMPO functionalized polythiophene thin films

Kunz, Tamara K.; Wolf, Michael O.

doi:10.1039/c0py00308e

Cited by 41 publications

(36 citation statements)

References 37 publications

(10 reference statements)

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“…The vast majority of research towards stable radical polymers has been motivated by their utility as electrode materials in batteries, where the introduction of conductive (nano)fillers has led to enhanced performance . However, radical polymers have also shown application as high‐spin ground state materials, (co)catalysts for the selective oxidation of alcohols, inhibitors of self‐polymerization reactions, solid‐state conductive materials, and the functional component of memory architectures …”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization, and thin‐film properties of 6‐oxoverdazyl polymers prepared by ring‐opening metathesis polymerization

Paquette

Ezugwu

Yadav

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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Redox-active 6-oxoverdazyl polymers were synthesized via ring-opening metathesis polymerization (ROMP) and their solution, bulk, and thin-film properties investigated. Detailed studies of the ROMP method employed confirmed that stable radical polymers with controlled molecular weights and narrow molecular weight distributions (Ð < 1.2) were produced. Thermal gravimetric analysis of a representative example of the title polymers demonstrated stability up to 190 °C, while differential scanning calorimetry studies revealed a glass transition temperature of 152 C. Comparison of the spectra of 6-oxoverdazyl monomer 12 and polymer 13, including FT-IR, UV-vis absorption, and electron paramagnetic resonance spectroscopy, was used to confirm the tolerance of the ROMP mechanism for the 6-oxoverdazyl radical both qualitatively and quantitatively.Cyclic voltammetry studies demonstrated the ambipolar redox properties of polymer 13 (E 1/2,ox = 0.25 and E 1/2,red = −1.35 V relative to ferrocene/ferrocenium), which were consistent with those of monomer 12. The charge transport properties of thin films of polymer 13 were studied before and after a potential of 5 V was applied, revealing a drastic drop in the resistivity from 10 6 10 10 m or more to 1.7  10 4 m and suggesting the potential usefulness of polymer 13 in bistable electronics.

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Section: Introductionmentioning

confidence: 99%

Synthesis, characterization, and thin‐film properties of 6‐oxoverdazyl polymers prepared by ring‐opening metathesis polymerization

Paquette

Ezugwu

Yadav

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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“…In order to exploit these systems as radical polymers, open‐shell groups have been attached to pre‐synthesized polymer structures. A simple example of this is the click reaction between acetylene functionalized TEMPO and azide functionalized poly(3‐alkylthiopehene)s . Similar concepts have also been implemented to attach open‐shell moieties to more exotic architectures including siloxane backbones, cellulose, and dendritic systems .…”

Section: Radical Polymersmentioning

confidence: 99%

Recent advances in the syntheses of radical-containing macromolecules

Wingate

Boudouris

2016

J. Polym. Sci. Part A: Polym. Chem.

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Tailor-made polymers containing specific chemical functionalities have ushered in a number of emerging fields in polymer science. In most of these next-generation applications the focus of the community has centered upon closed-shell macromolecules. Conversely, macromolecules containing stable radical sites have been less studied despite the promise of this evolving class of polymers. In particular, radical-containing macromolecules have shown great potential in magnetic, energy storage, and biomedical applications. Here, the progress regarding the syntheses of open-shell containing polymers are reviewed in two distinct subclasses. In the first, the syntheses of radical polymers (i.e., materials composed of nonconjugated macromolecular backbones and with open-shell units present on the polymer pendant sites) are described. In the second, polyradical (i.e., macromolecules containing stabi-lized radical sites either within the macromolecular backbone or those containing radical sites that are stabilized through a large degree of conjugation) synthetic schemes are presented. Thus, the state-of-the-art in open-shell macromolecular syntheses will be reported and future means by which to advance the current archetype will be discussed. By detailing the synthetic pathways possible for, and the inherent synthetic limitations of, the creation of these functional polymers, the community will be able to extend the bounds of the radical-containing macromolecular paradigm.

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“…TEMPO (2,2,6,6‐tetramethylpiperidine‐1‐oxyl‐4‐yl) compounds are redox active material and undergo an electrochemical redox reaction between their neutral and oxidized forms shown in Chart . Attempts to apply polymers having the TEMPO unit to electronic devices such as batteries have been made …”

Section: Introductionmentioning

confidence: 99%

“…Various polymers having the TEMPO unit in their side chains have been prepared, and their electrochemical responses have been investigated. Particularly, TEMPO polymers with π‐conjugated main chains are the subject of recent papers . They have been prepared by the addition polymerization of acetylenes with TEMPO pendant(s) or oxidative polymerization of pyrrole and thiophene with TEMPO pendant(s).…”

Section: Introductionmentioning

confidence: 99%

1,4‐Diiodobenzene with –COO–TEMPO (TEMPO = 2,2,6,6‐tetramethylpiperidine‐1‐oxyl‐4‐yl) substituents at 2,5‐positions: synthesis and use as a monomer for new π‐conjugated polymers having nitroxyl radicals in side chains

Iijima

Abe

Koizumi

et al. 2013

Polymers for Advanced Techs

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The reaction of 2,5-diiodo-1,4-benzenedicarbonyl chloride, C 6 H 2 I 2 (COCl) 2 -p, with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO-ol) gave I-Ph(COO-TEMPO) 2 -I, Monomer-1. Pd-catalyzed polycondensation of Monomer-1 with Me 3 Sn-Th-SnMe 3 (2,5-bis(trimethylstannyl)thiophene) and Bu 3 Sn-CH = CH-SnBu 3 (1,2-bis-(tributylstannyl)ethylene) gave the corresponding π-conjugated polymers, Polymer-1 and Polymer-2, respectively. Monomer-1 was converted to a diethynyl compound, H-C ≡ C-Ph(COO-TEMPO) 2 -C ≡ C-H (Monomer-1'), and Pd-catalyzed polycondensation between Monomer-1 and Monomer-1' gave a π-conjugated poly(arylene ethynylene) type polymer, Polymer-3. According to the expansion of the π-conjugation system by the polymerization, the UV-vis peaks of Monomer-1 (λ max = 323 nm) and Monomer-1' (327 nm) are shifted to longer wavelengths (λ max = 365 nm, 385 nm, and 396 nm for Polymer-1, Polymer-2, and Polymer-3, respectively). Polymer-1-Polymer-3 showed ESR signals at about g = 2.01 with reasonable intensities. They are electrochemically active and showed a peak current anodic (oxidation) peak at about 0.9 V versus Ag/AgCl, which is reasonable for TEMPO polymers.

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Electrodeposition and properties of TEMPO functionalized polythiophene thin films

Cited by 41 publications

References 37 publications

Synthesis, characterization, and thin‐film properties of 6‐oxoverdazyl polymers prepared by ring‐opening metathesis polymerization

Synthesis, characterization, and thin‐film properties of 6‐oxoverdazyl polymers prepared by ring‐opening metathesis polymerization

Recent advances in the syntheses of radical-containing macromolecules

1,4‐Diiodobenzene with –COO–TEMPO (TEMPO = 2,2,6,6‐tetramethylpiperidine‐1‐oxyl‐4‐yl) substituents at 2,5‐positions: synthesis and use as a monomer for new π‐conjugated polymers having nitroxyl radicals in side chains

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