Convenient Route To Initiate Kumada Catalyst-Transfer Polycondensation Using Ni(dppe)Cl<sub>2</sub> or Ni(dppp)Cl<sub>2</sub> and Sterically Hindered Grignard Compounds

Senkovskyy, Volodymyr; Sommer, Michael; Tkachov, Roman; Komber, Hartmut; Huck, Wilhelm T. S.; Kiriy, Anton

doi:10.1021/ma1024889

Cited by 101 publications

(129 citation statements)

References 48 publications

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“…This concept was shown to work nicely with o-bromomagesiotoluene and 2-bromomagnesio-3-hexylthiophene, which were reacted with NidpppCl 2 and NidppeCl 2 . [16] The use of these complexes in the polymerization of 1 finally resulted in complete incorporation of the initiator group as well as in a precise control of MW and polydispersity, as expected for bidentate phosphorous ligands. The versatility of this convenient method was further exemplified by the preparation of P3HT having an enlarged aromatic system with an electron deficient benzothiadiazole group (Scheme 3h).…”

Section: Ex Situ (External) Initiationmentioning

confidence: 91%

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

Kiriy

Senkovskyy

Sommer

2011

Macromol. Rapid Commun.

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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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Section: Ex Situ (External) Initiationmentioning

confidence: 91%

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

Kiriy

Senkovskyy

Sommer

2011

Macromol. Rapid Commun.

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225

178

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“…The dissociation of the catalyst species was accompanied by a decrease in catalyst activity leading to low polymer formation. To solve this problem, we were inspired by the work of a number of research groups, in which polymerization was externally initiated from an active tolyl-functionalized nickel complex 3 (Scheme 1) [8–9 22]. The tolyl–nickel species 3 is soluble and shows good stability in THF in an inert environment.…”

Section: Resultsmentioning

confidence: 99%

“…1). Matrix-assisted laser desorption ionization mass spectrometry (MALDIMS) and 1 H NMR experiments were used to determine the degree of end-group control in these polymerizations [8,26]. From the mass of the polymeric species and the distinctive proton resonance of the end-groups, it was possible to detect the presence of o -tolyl/H, H/H and Br/H end-groups (Fig.…”

Section: Resultsmentioning

confidence: 99%

Controlled synthesis of poly(3-hexylthiophene) in continuous flow

Seyler¹,

Subbiah²,

Jones³

et al. 2013

Beilstein J. Org. Chem.

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SummaryThere is an increasing demand for organic semiconducting materials with the emergence of organic electronic devices. In particular, large-area devices such as organic thin-film photovoltaics will require significant quantities of materials for device optimization, lifetime testing and commercialization. Sourcing large quantities of materials required for the optimization of large area devices is costly and often impossible to achieve. Continuous-flow synthesis enables straight-forward scale-up of materials compared to conventional batch reactions. In this study, poly(3-hexylthiophene), P3HT, was synthesized in a bench-top continuous-flow reactor. Precise control of the molecular weight was demonstrated for the first time in flow for conjugated polymers by accurate addition of catalyst to the monomer solution. The P3HT samples synthesized in flow showed comparable performance to commercial P3HT samples in bulk heterojunction solar cell devices.

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“…It should be noted that the initiator did contain excess dppp ligand, which may have had some influence, since any Ni(dppp) 2 formed in solution would be stable with respect to oxidative addition (and therefore reinitiation). Very recent reports by Sommer et al have highlighted a convenient route for the creation of stable initiator complexes by the reaction of phenyl or thienyl Grignard reagents bearing ortho alkyl groups with Ni(dppp)Cl 2 [69]. In this case, transmetallation occurs to displace one chlorine group so as to afford a stable Ni(II) complex that can be used as an initiator.…”

Section: Initiation and Catalyst Transfer Propagationmentioning

confidence: 99%

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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Convenient Route To Initiate Kumada Catalyst-Transfer Polycondensation Using Ni(dppe)Cl₂ or Ni(dppp)Cl₂ and Sterically Hindered Grignard Compounds

Cited by 101 publications

References 48 publications

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

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

Controlled synthesis of poly(3-hexylthiophene) in continuous flow

The Synthesis of Conjugated Polythiophenes by K umada Cross‐Coupling

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Convenient Route To Initiate Kumada Catalyst-Transfer Polycondensation Using Ni(dppe)Cl2 or Ni(dppp)Cl2 and Sterically Hindered Grignard Compounds

Cited by 101 publications

References 48 publications

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

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

Controlled synthesis of poly(3-hexylthiophene) in continuous flow

The Synthesis of Conjugated Polythiophenes by K umada Cross‐Coupling

Contact Info

Product

Resources

About

Convenient Route To Initiate Kumada Catalyst-Transfer Polycondensation Using Ni(dppe)Cl₂ or Ni(dppp)Cl₂ and Sterically Hindered Grignard Compounds