Within the limited number of reports on n-type polymers, naphthalene-diimide (NDI) and perylene diimide alternating main chain copolymers are currently evolving as an intriguing class of electron-conducting materials with electron-mobility up to 0.85 cm2/Vs. Typically, conventional step-growth polycondensations are used to synthesize rylene diimide based alternating copolymers, which result in a limited control over polymer MW and polydispersities.
We found out that activated Zn powder and Br-TNDIT-Br form anion-radical complexes instead of Br-TNDIT-ZnBr, conventional Zn-organic derivatives. These highly unusual zinc complexes undergo Ni-catalyzed chain-growth polymerization leading to conjugated polymer P(TNDT) with controlled MW, relatively narrow PDI and specific end-functions. semiconductors
- Senkovskyy, V. ; Tkachov, R. ; Komber, H. ; Sommer, M. ; Heuken, M. ; Voit, B. ; Huck, W. T. S. ; Kataev, V. ; Petr, A. ; Kiriy, A. Chain-growth polymerization of unusual anion-radical monomers based on naphthalene diimide: a new route to well-defined n-type conjugated copolymers Journal of the American Chemical Society 133 (2011) 19966-19970
- Senkovskyy, V. ; Tkachov, R. ; Komber, H. ; John, A. ; Sommer, J.-U. ; Kiriy, A. Mechanistic insight into catalyst-transfer polymerization of unusual anion-radical naphthalene diimide monomers: An observation of Ni(0) intermediates Macromolecules 45 (2012) 7770-7777
- Tkachov, R. ; Karpov, Y. ; Senkovskyy, V. ; Raguzin, I. ; Zessin, J. ; Lederer, A. ; Stamm, M. ; Voit, B. ; Beryozkina, T. ; Bakulev, V. ; Zhao, W. ; Facchetti, A. ; Kiriy, A. Efficient tin-free route to a donor-acceptor semiconducting copolymer with variable molecular weights. Macromolecules 47 (2014) 3845-3851
- Liu, W. ; Tkachov, R. ; Komber, H. ; Senkovskyy, V. ; Schubert, M. ; Wei, Z. ; Facchetti, A. ; Neher, D. ; Kiriy, A. Chain-growth polycondensation of perylene diimide-based copolymers: a new route to regioregular perylene diimide-based acceptors for all-polymer solar cells and n-type transistors more Polymer Chemistry 5 (2014) 3404-3411