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

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• 作者：Volodymyr Senkovskyy ; Roman Tkachov ; Hartmut Komber ; Andreas John ; Jens-Uwe Sommer ; Anton Kiriy
• 刊名：Macromolecules
• 出版年：2012
• 出版时间：October 9, 2012
• 年：2012
• 卷：45
• 期：19
• 页码：7770-7777
• 全文大小：377K
• 年卷期：v.45,no.19(October 9, 2012)
• ISSN：1520-5835

文摘

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鈥?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.