A Robust Electroactive n-Dopable Aromatic Polyketone

Chiechi, Ryan C.; Sönmez, Gürsel; Wudl, Fred

doi:10.1002/adfm.200400291

Cited by 19 publications

(26 citation statements)

References 20 publications

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“…We previously observed this process via spectroelectrochemistry in transient CPIs. 4 In this paper, we rely on a combination of experiment and calculation to show that the same effect is present in PFC. However, proving that spinless doping does not induce spontaneous spin un-pairing and that CPIs are semiconductors is not straightforward.…”

Section: Spinless Dopingmentioning

confidence: 99%

“…This two-step conversion enabled us to qualitatively follow the conversion of the polymer analogous reaction spectroscopically. To render PFC sufficiently soluble in organic solvents, and to prevent overly strong binding of counter-ions, we isolated PFC as the BF 4 À salt by rst trapping free PFC with methoxide to form the non-conjugated methyl ether (i.e., with CH 3 O À as shown in Scheme 1), dissolving it in aqueous HBF 4 , and repeatedly extracting it with CH 2 Cl 2 . We encountered difficulties obtaining clean 1 H-NMR spectra of PFC due to problems with locking and shimming (see ESI † for examples) possibly due to the combination of the ionic and polymeric nature of CPIs driving aggregation in organic solvents (PFC is sparingly soluble in CDCl 3 ).…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

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Stabilizing cations in the backbones of conjugated polymers

et al. 2014

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We synthesized a cross-conjugated polymer containing ketones in the backbone and converted it to a linearly conjugated, cationic polyarylmethine via a process we call "spinless doping" to create a new class of materials, conjugated polyions. This process involves activating the ketones with a Lewis acid and converting them to trivalent cations via the nucleophilic addition of electron-rich aryl moieties. Spinless doping lowers the optical band gap from 3.26 to 1.55 eV while leaving the intrinsic semiconductor properties of the polymer intact. Electrochemical reduction (traditional doping) further decreases the predicted gap to 1.18 eV and introduces radicals to form positive polarons; here, n-doping produces a p-doped polymer in its metallic state. Treatment with a nucleophile (NaOMe) converts the cationic polymer to a neutral, non-conjugated state, allowing the band gap to be tuned chemically, postpolymerization. The synthesis of these materials is carried out entirely without the use of Sn or Pd and relies on scalable Friedel-Crafts chemistry

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Section: Spinless Dopingmentioning

confidence: 99%

Section: Synthesis and Characterizationmentioning

confidence: 99%

Stabilizing cations in the backbones of conjugated polymers

et al. 2014

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“…We observed similar, albeit more pronounced, doping behavior in PTK. 8 A plausible reason why the reduction behavior in PTFK appears concealed is the broad -D and, consequently, large range of accessible states leading to gradual changes in conductivity.…”

Section: Optoelectronic Characterizationmentioning

confidence: 99%

“…However, these charges are transient and exist only under a negative bias or under strongly acidic conditions. 8 The general route towards intrinsic CPIs is to render a cross-conjugated polyketone fully conjugated by the addition of nucleophiles via "spinless doping" in a post-polymerization modification. 9 This process extends the conjugation of the polymer and imparts cationic character, allowing water to solvate the backbone.…”

Section: Introductionmentioning

confidence: 99%

Cross-Conjugated n-Dopable Aromatic Polyketone

Voortman¹,

Bartesaghi

Koster³

et al. 2015

Macromolecules

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This paper describes the synthesis and characterization of a high molecular weight cross-conjugated polyketone synthesized via scalable Friedel-Crafts chemistry. Crossconjugated polyketones are precursors to conjugated polyions; they become orders of magnitude more conductive after a two-electron reduction and demonstrate reversible spinless doping upon protonation with acids. Cross-conjugated polyketones are a new polymer platform that posses the same optoelectronic tunability as conventional polymers but with excellent thermal-and oxidative stability. We constructed a proof-ofconcept organic light-emitting diode device and demonstrate that a cross-conjugated polyketone can be successfully used as an n-dopable semiconducting material.

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“…These polymers typically exhibit high glass transition temperatures and high melting points [17], which makes them ideal candidates for use as stationary phase in chromatography applications. Aromatic polyketones are synthesized by Friedel-Crafts or nucleophilic aromatic substitution reactions [20][21][22][23][24][25]. The materials are usually insolu-ble and intractable.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of a series of soluble main-chain chiral nonracemic poly(alkyl-aryl ketone)

Wei¹,

Wang²,

Wu³

et al. 2008

Express Polym. Lett.

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Abstract.A series of main-chain chiral polyketones have been synthesized through condensation polymerization of a dihalide and a diketone with optically pure binaphthyl moiety as linkage in the polymer backbone. The solubility of the polymers can be easily enhanced by substituents at the alpha position next to the carbonyl groups. Reducing the steric hindrance of the substituents in the monomers increases the reactivity of the polymerization. The chiral polymers exhibit large optical rotations. Circular Dichroism (CD) spectra of the polymers are similar to those of the corresponding monomers. The novel synthetic strategy may have great impact on future development of palladium catalyzed condensation polymerizations. The highly soluble chiral polymers synthesized allow for preparation of materials in the form of thin films and have potentials applications in various areas such as chiral separation and recognition.

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A Robust Electroactive n-Dopable Aromatic Polyketone

Cited by 19 publications

References 20 publications

Stabilizing cations in the backbones of conjugated polymers

Stabilizing cations in the backbones of conjugated polymers

Cross-Conjugated n-Dopable Aromatic Polyketone

Synthesis of a series of soluble main-chain chiral nonracemic poly(alkyl-aryl ketone)

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