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Issue 41, 2013
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Role of the transition metal in Grignard metathesis polymerization (GRIM) of 3-hexylthiophene

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Abstract

Regioregular poly(3-alkylthiophene)s are widely used in organic electronics applications such as solar cells and field effect transistors. Nickel, palladium, and platinum diphenylphosphinoethane complexes were tested as catalysts for the Grignard metathesis (GRIM) polymerization of 2,5-dibromo-3-hexylthiophene and 2-bromo-5-iodo-3-hexylthiophene. Nickel-mediated polymerization generated regioregular, low-polydispersity poly(3-hexylthiophene) with well-defined molecular weight consistent with a “living” chain-growth mechanism. By contrast, palladium-mediated polymerization proceeded by a step-growth mechanism and generated polymers with less than 80% head-to-tail couplings. Platinum-mediated polymerization gave very low molecular weight products. Kinetic and computational results suggested that the nickel catalyst acts as an initiator and remains associated with the growing polymer chain, while palladium dissociates from the growing chain. Computational and experimental evidence was provided for various side reactions of dissociated Pd(0) catalyst, which could yield a step growth mechanism and lower regioirregularity.

Graphical abstract: Role of the transition metal in Grignard metathesis polymerization (GRIM) of 3-hexylthiophene

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Publication details

The article was received on 16 Aug 2013, accepted on 06 Sep 2013 and first published on 09 Sep 2013


Article type: Paper
DOI: 10.1039/C3TA13258G
Citation: J. Mater. Chem. A, 2013,1, 12841-12849
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    Role of the transition metal in Grignard metathesis polymerization (GRIM) of 3-hexylthiophene

    M. P. Bhatt, H. D. Magurudeniya, P. Sista, E. E. Sheina, M. Jeffries-EL, B. G. Janesko, R. D. McCullough and M. C. Stefan, J. Mater. Chem. A, 2013, 1, 12841
    DOI: 10.1039/C3TA13258G

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