"Living" conjugated polymers: a new approach in engineering of complex materials for needs of organic electronics
Zusammenfassung der Projektergebnisse
The present project was devoted to study of chain-growth Kumada polycondensation, exploring its scope toward involvement of more complex monomers and further development of KCTP-based surface-initiated polymerization. Major project tasks were successfully accomplished. Furthermore, the project scope was extended much beyond the initial tasks. Particularly, important attention was paid to mechanistic investigations because it was recognized that a lack of understanding of chemical processes underlying KCTP is important obstacle precluding further developments. Particularly, mechanistic details of the intramolecular catalyst-transfer process (responsible for the chain-growth, near living propagation) was studied. Unexpectedly, an intriguing catalyst-ring walking mechanism was discovered. The scope of Kumada-based SIP was significantly extended. Particularly, fluorene-based monomer was involved into the grafting process which resulted into hairy PFO microparticles with interesting optical properties. The method to grow conjugated polyelectrolyte shell was developed which resulted into responsive microparticles suitable for sensing application. Significant progress was achieved in development of initiation process – i) new bifunctional initiator was prepared; ii) convenient route to initiate KCTP from readily available source was developed. For the first time, electrondeficient monomers were involved into chain-growth KCTP which allowed controlled preparation of very promising NDI-based copolymer with controlled molecular weight. The progress achieved was reviewed in invited Feature article published in Macromolecular Rapid communication. As such, the project contributed substantially to the development of very useful polymerization tool for preparation of well-defined conjugated polymers for various optoelectronic applications.
Projektbezogene Publikationen (Auswahl)
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Microparticle-Supported Conjugated Polyelectrolyte Brushes Prepared via Surface-Initiated Kumada Catalyst Transfer Polycondensation for Sensor Application. Macromol. Rapid Commun. 2010, 31, 2146–2150
Tkachov, R.; Senkovskyy, V.; Oertel, U.; Synytska, A.; Horecha M.; Kiriy, A.
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Surface-initiated Kumada catalyst-transfer polycondensation of poly(9,9-dioctylfluorene) from organosilica particles: chain-confinement promoted b-phase formation. Chem. Commun. 2010, 46, 1425-1427
Tkachov R.; Senkovskyy, V.; Horecha, M.; Oertel, U.; Stamm, M.; Kiriy, A.
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Synthesis of a Bifunctional Initiator for Controlled Kumada Catalyst-Transfer Polycondensation/Nitroxide-Mediated Polymerization and Preparation of Poly(3-hexylthiophene)-Polystyrene Block Copolymer Therefrom. Macromolecules 2010, 43, 77-81
Kaul, E.; Senkovskyy, V.; Tkachov R.; Bocharova, V.; Komber, H.; Stamm, M.; Kiriy, A.
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Chain-Growth Polymerization of Unusual Anion-Radical Monomers Based on Naphthalene Diimide: A New Route to well-defined n-Type Conjugated Copolymers. J. Am. Chem. Soc. 2011, 133, 19966–19970
Senkovskyy, V.; Tkachov, R.; Komber, H.; Sommer, M.; Heuken, M.; Voit, B.; Huck, W. T. S.; Kataev, V.; Petr, A.; Kiriy, A.
