Mechanistic Insight into Catalyst-Transfer Polymerization of Unusual Anion-Radical Naphthalene Diimide Monomers: An Observation of Ni(0) Intermediates

Ni-catalyzed polymerization of anion-radical complexes formed upon mixing of 2,6-bis(2-bromothien-5-yl)naphthalene-1,4,5,8-tetracarboxylic-N,N′-bis(2-octyldodecyl) diimide and activated Zn powder was investigated. We provide experimental evidence that the polymerization involves the chain-growth mec...

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Bibliographic Details
Published in:Macromolecules 2012-10, Vol.45 (19), p.7770-7777
Main Authors: Senkovskyy, Volodymyr, Tkachov, Roman, Komber, Hartmut, John, Andreas, Sommer, Jens-Uwe, Kiriy, Anton
Format: Article
Language:English
Subjects:
Applied sciences
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Polymers with particular properties
Preparation, kinetics, thermodynamics, mechanism and catalysts
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Summary:Ni-catalyzed polymerization of anion-radical complexes formed upon mixing of 2,6-bis(2-bromothien-5-yl)naphthalene-1,4,5,8-tetracarboxylic-N,N′-bis(2-octyldodecyl) diimide and activated Zn powder was investigated. We provide experimental evidence that the polymerization involves the chain-growth mechanism and proceeds via Ni(0) complexes which were previously proposed to be key intermediates in other chain-growth catalyst-transfer polycondensations (CTPs), such as Kumada CTP of thiophenic monomers. DFT calculations predict a remarkable stability of the naphthalene diimide-based Ni(0) complexes. A plausible polymerization mechanism is proposed.
ISSN:0024-9297
1520-5835
DOI:10.1021/ma301797w