Grignard Metathesis Chain-Growth Polymerization for Poly(bithienylmethylene)s: Ni Catalyst Can Transfer across the Nonconjugated Monomer

Sheng, Wu; Sun, Yi; Huang, Li; Wang, Jianwei; Zhou, Yihan; Geng, Yanhou

doi:10.1021/ma100537d

Cited by 47 publications

(46 citation statements)

References 35 publications

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“…In order to assure mono-metallation in the monomer, such that no ''communication'' could occur between both halides, an iodo-bromo-functionalized monomer was used. The polymerization showed a chain growth character that had a high level of control (M n 55 kDa, PDI = 1.2) and was further proven by the preparation of block copolymers with 3-hexylthiophene, by sequential monomer addition [74]. End group analysis using MALDI showed the H/Br end groups to be dominant, and this was consistent with the chain growth mechanism.…”

Section: Initiation and Catalyst Transfer Propagationsupporting

confidence: 59%

The Synthesis of Conjugated Polythiophenes by K umada Cross‐Coupling

Koch

Heeney

2012

Materials Science and Technology

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Conjugated polymers have been the subject of intensive research efforts over the past few decades. Much of this interest has stemmed from the fact that such materials combine the inherent processibility and mechanical robustness associated with polymers, with the electronic properties more typically associated with inorganic semiconductors. Thus, such materials may allow the fabrication of electronic devices on a variety of flexible or conformable surfaces, by a range of potentially low-cost and large-area deposition techniques such as printing. Possible applications include field effect transistors for display backplanes, organic solar cells, electrochromic displays, chemical sensors, and polymeric light-emitting diodes [1].Within the realms of conjugated polymer research, thiophene-containing materials have been one of the most widely investigated classes for many of the above applications [2,3]. Thiophene is a cheap and widely available electron-rich, planar aromatic heterocycle which is readily functionalized by range of chemistries. As a result, it can be copolymerized with a variety of aromatic comonomers to generate polymers with extended π-electron delocalization along the backbone. The alternating double and single bonds of the delocalized conjugated system are nondegenerate, leading to an energy band gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). For many of the optoelectronic applications outlined above, the absolute energy levels of the HOMO and LUMO, as well as the band gap between them, are important parameters affecting device performance. As such, major research efforts have been devoted to understanding how chemical structure can influence the electronic delocalization of conjugated polymers. Whilst these factors are complex, they can be related to points such as the attachment of electron-donating/-withdrawing substituents to the polymer backbone, the degree of backbone planarity (and, therefore, the π-electron overlap and delocalization), and the nature and aromaticity of any comonomers included in the polymer backbone.

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Section: Initiation and Catalyst Transfer Propagationsupporting

confidence: 59%

The Synthesis of Conjugated Polythiophenes by K umada Cross‐Coupling

Koch

Heeney

2012

Materials Science and Technology

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“…Thus, KCTP not only follows the chain-growth mechanism but even displays the characteristics of a ''living'' polymerization process. [62] While we and several other research groups have confirmed the chain-growth mechanism for the KCTP of 1 [22,24,63,64] and other monomers, [28][29][30][31][65][66][67] Achord and Rawlins [68] reported data that contradict the observations of the livingness of KCTP. [24,69] General Mechanism…”

Section: Assessment Of the Chain-growth Mechanismmentioning

confidence: 52%

“…Some portion of such ''unoriented'' Ni(0) species may reach the terminal phenyl-or thiophenebromine bond at the opposite chain end and start polymerization there. An intriguing aspect of the catalyst transfer process was recently revealed by Geng and coworkers [66] who demonstrated KCTP of a non-conjugated monomer. Their polymerization conditions proceeded in a chain-growth manner so that even the preparation of block copolymers was possible.…”

Section: Chain-propagationmentioning

confidence: 99%

Kumada Catalyst‐Transfer Polycondensation: Mechanism, Opportunities, and Challenges

Kiriy

Senkovskyy

Sommer

2011

Macromol. Rapid Commun.

225

178

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Kumada catalyst-transfer polycondensation (KCTP) is a new but rapidly developing method with great potential for the preparation of well-defined conjugated polymers (CPs). The recently discovered chain-growth mechanism is unique among the various transition metal-catalyzed polycondensations, and has thus attracted much attention among researchers. Most progress is found in the areas of mechanism and external initiation via new initiators, but also the number of monomers other than thiophene that can be polymerized is steadily increasing. Accordingly, the variety of CP chain architectures is increasing as well, and a considerable contribution of KCTP toward more efficient materials can be expected in the future. This review critically focuses on very recent progress in the synthesis of CPs and the mechanism of KCTP, and is finally aimed at providing a comprehensive picture of this exciting polymerization method.

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“…One can imagine that the catalyst may be able to transfer across the neighboring aromatic rings that are nonconjugated but appropriately arranged in space, thus KCGP is also applicable to the synthesis of nonconjugated polymers. Geng et al demonstrated this speculation with a bithienylmethane derivative (12) as the monomer, in which two thiophene rings are connected via a saturated carbon ( Figure 10) [55]. They found that both Ni(dppp)Cl 2 and Ni(dppe)Cl 2 gave poly(bithienylmethylene) (PBTM) with narrow PDI.…”

Section: -System and Transfer To The Chain Terminus Via "Ring Walking"mentioning

confidence: 98%

Kumada chain-growth polycondensation as a universal method for synthesis of well-defined conjugated polymers

et al. 2010

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Kumada chain-growth polycondensation (KCGP) is a novel method for the synthesis of well-defined conjugated polymers. Because the Ni-catalyst can transfer in an intramolecular process to the propagating chain end, the polymerization follows chain-growth mechanism. With this newly developed method, various conjugated polymers, such as polythiophenes, poly(p-phenylene) (PPP), polypyrrole (PPy), and polyfluorene with controlled molecular weights and relatively narrow polydispersities (PDIs), have been prepared. Especially, the polymerizations for poly(3-alkylthiophene)s (P3ATs), PPP, and PPy exhibited quasi-living characteristics, which allows preparing polymer brushes, fully-conjugated block copolymers, and macroinitiators and macro-reactants for the synthesis of rod-coil block copolymers. In the current review, the progress in this new area is summarized.

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Grignard Metathesis Chain-Growth Polymerization for Poly(bithienylmethylene)s: Ni Catalyst Can Transfer across the Nonconjugated Monomer

Cited by 47 publications

References 35 publications

The Synthesis of Conjugated Polythiophenes by K umada Cross‐Coupling

The Synthesis of Conjugated Polythiophenes by K umada Cross‐Coupling

Kumada Catalyst‐Transfer Polycondensation: Mechanism, Opportunities, and Challenges

Kumada chain-growth polycondensation as a universal method for synthesis of well-defined conjugated polymers

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