Insights in the Ni-thiophene association in the synthesis of thiophene-para-phenylene block copolymers via Kumada catalyst transfer condensative polymerization

Ceunen, Ward; Winter, Julien De; Gerbaux, Pascal; Koeckelberghs, Guy

doi:10.1016/j.eurpolymj.2019.109311

Cited by 5 publications

(2 citation statements)

References 45 publications

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“…Since the thiophene monomer is a comparatively stronger π-donor than the phenylene monomer, the order of addition to the nickel catalyst is critical to reaction success. [45][46][47] As such, the PPP monomer was polymerized first by adding iPrMgCl•LiCl to a THF solution of 1,4-dibromo-2,5-bis(2-ethylhexyloxy)benzene followed by addition of Ni(o-tolyl)(dppe)Cl which resulted in formation of the PPP homopolymers with a living chain end (Schemes S2 and S3 †). Grignard-activated 2,5-dibromo-3-hexylthiophene monomer was then added to the living PPP solution to afford P3HT-b-PPP BCPs.…”

Section: Synthesis and Characterization Of P3ht N -B-ppp M Bcpsmentioning

confidence: 99%

Crystallization-driven self-assembly of poly(3-hexylthiophene)-b-poly(2,5-bis(2-ethylhexyloxy)p-phenylene), a π-conjugated diblock copolymer with a rigid rod corona-forming block

Vespa,

MacFarlane,

Hudson

et al. 2024

Polym. Chem.

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Section: Synthesis and Characterization Of P3ht N -B-ppp M Bcpsmentioning

confidence: 99%

Crystallization-driven self-assembly of poly(3-hexylthiophene)-b-poly(2,5-bis(2-ethylhexyloxy)p-phenylene), a π-conjugated diblock copolymer with a rigid rod corona-forming block

Vespa,

MacFarlane,

Hudson

et al. 2024

Polym. Chem.

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“…An important aspect of synthetic tunability is the ability to change the conjugated backbone itself, by the incorporation of two or more different monomers into a copolymer. For example, Havinga et al first demonstrated the spectral engineering of π-conjugated polymers using a donor–acceptor approach, whereby combining an electron-rich donor with a high-lying highest occupied molecular orbital (HOMO) level and an electron-deficient acceptor with a low-lying lowest unoccupied molecular orbital (LUMO) level shifts the optical absorbance of the copolymer to a lower energy, corresponding to a narrower band gap, in comparison to the constituent donor and acceptor homopolymers. , A persistent challenge of controlled copolymer synthesis is the sensitivity to the order of monomer addition for many catalytic systems, which limits the complexity of backbone architecture that can be achieved. − …”

Section: Copolymersmentioning

confidence: 99%

Precision Synthesis of Conjugated Polymers Using the Kumada Methodology

2021

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Conspectus Since the discovery of conductive poly(acetylene), the study of conjugated polymers has remained an active and interdisciplinary frontier between polymer chemistry, polymer physics, computation, and device engineering. One of the ultimate goals of polymer science is to reliably synthesize structures, similar to small molecule synthesis. Kumada catalyst-transfer polymerization (KCTP) is a powerful tool for synthesizing conjugated polymers with predictable molecular weights, narrow dispersities, specific end groups, and complex backbone architectures. However, expanding the monomer scope beyond the well-studied 3-alkylthiophenes to include electron-deficient and complex heterocycles has been difficult. Revisiting the successful applications of KCTP can help us gain new insight into the CTP mechanisms and thus inspire breakthroughs in the controlled polymerization of challenging π-conjugated monomers. In this Account, we highlight our efforts over the past decade to achieve controlled synthesis of homopolymers (p-type and n-type), copolymers (diblock and statistical), and monodisperse high oligomers. We first give a brief introduction of the mechanism and state-of-the-art of KCTP. Since the extent of polymerization control is determined by steric and electronic effects of both the catalyst and monomer, the polymerization can be optimized by modifying monomer and catalyst structures, as well as finding a well-matched monomer–catalyst system. We discuss the effects of side-chain steric hindrance and halogens in the context of heavy atom substituted monomers. By moving the side-chain branch point one carbon atom away from the heterocycle to alleviate steric crowding and stabilize the catalyst resting state, we were able to successfully control the polymerization of new tellurophene monomers. Inspired by innocent role of the sterically encumbered 2-transmetalated 3-alkylthiophene monomer, we introduce the treatment of hygroscopic monomers with a bulky Grignard compound as a water-scavenger for the improved synthesis of water-soluble conjugated polymers. For challenging electron-deficient monomers, we discuss the design of new Ni(II)diimine catalysts with electron-donating character which enhance the stability of the association complex between the catalyst and the growing polymer chain, resulting in the quasi-living synthesis of n-type polymers. Beyond n-type homopolymers, the Ni(II)diimine catalysts are also capable of producing electron-rich and electron-deficient diblock and statistical copolymers. We discuss how density functional theory (DFT) calculations elucidate the role of catalyst steric and electronic effects in controlling the synthesis of π-conjugated polymers. Moreover, we demonstrate the synthesis of monodisperse high oligomers by temperature cycling, which takes full advantage of the unique character of KCTP in that it proceeds through distinct intermediates that are not reactive. The insight we gained thus far leads to the first example of isolated living conjugated polymer chains prepar...

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Disparity between rate and selectivity in the controlled synthesis of gradient conjugated copolymers

Van Oosten,

Matz,

Parravicini

et al. 2024

European Polymer Journal

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Insights in the Ni-thiophene association in the synthesis of thiophene-para-phenylene block copolymers via Kumada catalyst transfer condensative polymerization

Cited by 5 publications

References 45 publications

Crystallization-driven self-assembly of poly(3-hexylthiophene)-b-poly(2,5-bis(2-ethylhexyloxy)p-phenylene), a π-conjugated diblock copolymer with a rigid rod corona-forming block

Crystallization-driven self-assembly of poly(3-hexylthiophene)-b-poly(2,5-bis(2-ethylhexyloxy)p-phenylene), a π-conjugated diblock copolymer with a rigid rod corona-forming block

Precision Synthesis of Conjugated Polymers Using the Kumada Methodology

Disparity between rate and selectivity in the controlled synthesis of gradient conjugated copolymers

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