Radical Copolymerization of 2,4-Disubstituted Enynes with Electron-Accepting Comonomers

Ochiai, Bungo; Tomita, Ikuyoshi; Endō, Takeshi

doi:10.1021/ma010702o

Cited by 4 publications

(3 citation statements)

References 14 publications

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“…The polymer generated at 90 °C was believed to result from the polymerization of terminal diacetylenic moieties and/or silicon-bound enyne moieties, in agreement with other reports on the polymerization of diacetylene monomers 280−283 and aromatic enynes. 284,285 The so-produced electroactive films exhibited an equivalent surface coverage of TTF exceeding 2.0 × 10 −8 mol cm −2 (Figure 16c). Such a polymerization route involving butadiyne segments is particularly attractive because it provides convenient access to surface-bound electroactive polymers with considerably enhanced chemical and thermal stability, as already demonstrated for gold-grafted polydiacetylenic monolayers.…”

Section: Chemical Reviewsmentioning

confidence: 99%

Functionalization of Oxide-Free Silicon Surfaces with Redox-Active Assemblies

2016

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This review provides a comprehensive survey of the derivatization of hydrogen-terminated, oxide-free silicon surfaces with electroactive assemblies (from molecules to polymers) attached through strong interactions (covalent, electrostatic, and chimisorption). Provided that surface modification procedures are thoroughly optimized, such an approach has appeared as a promising strategy toward high-quality functional interfaces exhibiting excellent chemical and electrochemical stabilities. The attachment of electroactive molecules exhibiting either two stable redox states (e.g., ferrocene and quinones) or more than two stable redox states (e.g., metalloporphyrins, polyoxometalates, and C60) is more particularly discussed. Attention is also paid to the immobilization of electrochemically polymerizable centers. Globally, these functional interfaces have been demonstrated to show great promise for the molecular charge storage and information processing or the elaboration of the electrochemically switchable devices. Besides, there are also some relevant examples dealing with their activity for other fields of interest, such as sensing and electrochemical catalysis.

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Section: Chemical Reviewsmentioning

confidence: 99%

Functionalization of Oxide-Free Silicon Surfaces with Redox-Active Assemblies

2016

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“…In the latter case, the generated polymer is believed to result from the polymerization of terminal diacetylenic moieties and/or silicon-bound enyne moieties, in agreement with previous studies on the polymerization of diacetylene monomers 36−43 and aromatic enynes. 44,45 It has been demonstrated that the polymer materials derived from tailor-made diacetylene derivatives showed interesting optical, spectral, and electronic properties (e.g., stress-induced colorimetric and fluorogenic transitions, sensing capabilities). 37 Moreover, a large palette of structurally organized architectures, such as supramolecular assemblies and ordered nanostructures, could be generated from these functional units.…”

Section: Introductionmentioning

confidence: 99%

Controlled Grafting of Tetrathiafulvalene (TTF) Containing Diacetylenic Units on Hydrogen-Terminated Silicon Surfaces: From Redox-Active TTF Monolayer to Polymer Films

et al. 2012

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International audienceA tetrathiafulvalene (TTF)-terminated butadiyne derivative was synthesized and used for the preparation of redox-active TTF-modified hydrogen-terminated oxide-free silicon (Si−H) surfaces. TTF monolayer-modified silicon surfaces were produced when low grafting temperatures were used (typically 45 °C), whereas higher temperatures (90 °C) led to TTF polymer-modified surfaces. IR spectroscopy characterization provided evidence that TTF units bound to the surface through the formation of enyne linkers via hydrosilylation of the terminal alkyne bond. The TTF monolayers prepared at 45 °C were densely packed with a surface coverage of ca. 5.4 × 10−10 mol of TTF per cm2. For such systems, electrochemical measurements showed the redox signature of the bound TTF centers characterized by two reversible one-electron systems at ca. 0.40 and 0.73 V versus saturated calomel electrode (SCE). High values of electron-transfer rate constants were determined (>200 s−1) and ascribed to the presence of the conjugated bridge between the attached redox-active center and the underlying silicon surface. The TTF polymer-modified surfaces prepared at 90 °C resulted from the direct grafting of polymeric structures on Si−H and/or the postattachment functionalization of the preformed TTF monolayer. Polymerization process of the TTF-terminated butadiyne derivative was also investigated in solid state by means of differential scanning calorimetry and diffuse reflectance IR spectroscopy measurements

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“…The controlled polymerization of highly unsaturated monomers plays an important role in the synthesis of well‐defined polymers with unsaturated moieties that are applicable as functional and reactive polymers. For this reason, many efforts have been made to develop precisely controlled polymerizations of, for instance, conjugated dienes,1, 2 allenes,3–5 acetylenes,6–8 and conjugated enynes 9–13. Among them, conjugated enynes are attractive monomers because the controlled polymerization of enynes is expected to give polymers with acetylene, allene, and diene moieties.…”

Section: Introductionmentioning

confidence: 99%

Anionic polymerization of 4-phenyl-1-buten-3-yne derivatives bearing electron-withdrawing groups

Ochiai

Tomita

Endō

2001

J. Polym. Sci. A Polym. Chem.

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The anionic polymerization of derivatives of 4‐phenyl‐1‐buten‐3‐yne was carried out to investigate the effect of substituents on the polymerization behavior. The polymerization of 4‐(4‐fluorophenyl)‐1‐buten‐3‐yne and 4‐(2‐fluorophenyl)‐1‐buten‐3‐yne in tetrahydrofuran at −78 °C with n‐BuLi/sparteine as an initiator gave polymers consisting of 1,2‐ and 1,4‐polymerized units in quantitative yields with ratios of 80/20 and 88/12, respectively. The molecular weights of the polymers were controlled by the ratio of the monomers to n‐BuLi, and the distribution was relatively narrow (weight‐average molecular weight/number‐average molecular weight < 1.2), supporting the living nature of the polymerization. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1016–1023, 2001

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Radical Copolymerization of 2,4-Disubstituted Enynes with Electron-Accepting Comonomers

Cited by 4 publications

References 14 publications

Functionalization of Oxide-Free Silicon Surfaces with Redox-Active Assemblies

Functionalization of Oxide-Free Silicon Surfaces with Redox-Active Assemblies

Controlled Grafting of Tetrathiafulvalene (TTF) Containing Diacetylenic Units on Hydrogen-Terminated Silicon Surfaces: From Redox-Active TTF Monolayer to Polymer Films

Anionic polymerization of 4-phenyl-1-buten-3-yne derivatives bearing electron-withdrawing groups

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