Precise synthesis of well-defined electron conducting and donor-acceptor semiconducting copolymers for organic electronics
Synthesis and Properties of Functional Materials
Final Report Abstract
The project aimed to develop a chain-growth polycondensation of electron-deficient monomers and their copolymerization with electron-rich monomers, to synthesize 1) well-defined donoracceptor homopolymers with specific starting- and end-groups and 2) all-conjugated block copolymers (BCPs). To realize these goals, polymerizations of electron-deficient monomers, e.g., naphthalene diimide-based Br-TNDIT-Br/Zn and isoindigo-based Br-TiIT-Br/Zn, and electron-rich monomers, were investigated. “New generation” Buchwald-type Pd catalysts and initiators having bulky electron-rich ligands were tested in polymerization of the model monomer Br-TNDIT-Br/Zn. In all these cases, resulting polymers were characterized by very broad polydispersity and the polymerizations having, in most cases, a step-growth character. Only one ligand having two tBu3 groups and one aromatic moiety, showed a promising performance (signs of the chain-growth), however the polymerization was not controlled also in this case. This was a disappointing result, but the good outcome was that the polymerization with the catalyst 4 and initiators on its basis, allowed for incorporation of reactive starting groups (e.g., acetylene). This opened up a possibility for preparation of useful polymer architectures by a Huigen-type click chemistry, such as of donoracceptor BCPs, preparation of which was demonstrated in the present project. We suggest that the somewhat negative outcome, obtained in the middle of the project, was caused by highly challenging, ambitious tasks of the project, and we are sure that we made our best in attempts to accomplish successfully the project goals. Because of unexpected obstacles, the initial goals were adjusted and an alternative strategy to BCPs comprising conjugated polymers was developed. The new strategy to BCPs assumed incorporation of reactive end groups into π-conjugated polymers followed by their coupling with another polymer of interest. This strategy was implemented in the synthesis of a series of ultra-soft and high mobility BCPs comprising stateof-the-art semiconducting block (diketopyrrolopyrrole-based) and one of the best elastic component (PDMS). Outstanding characteristics for the BCP PDPP-TT–PDMS-25k, comprising 65 wt% of the elastic block, were obtained: hole mobility of 0.1 cm2 V^-1 s^-1, which is in the range of the fully conjugated reference polymer PDPP-TT (0.7 cm2 V^-1 s^-1), and a low elastic modulus of 5 MPa, which is in the range of mammalian tissue. This BCP exhibits an excellent stretchability and extraordinary durability, maintaining the initial electric conductivity in a doped state after 1500 cycles to 50% strain. The obtained materials are attractive materials for use in skin-compatible electronics. In conclusion, although there were some deviations from the initial research plan, the most general project goals were achieved successfully.
Publications
- Copolymerization of zincactivated isoindigo- and naphthalene-diimide based monomers: an efficient route to low bandgap π-conjugated random copolymers with tunable properties. Polym. Chem. 2016, 7, 2691–2697
Karpov, Y.; Maiti, J.; Tkachov, R.; Beryozkina, T.; Bakulev, V.; Liu, W.; Komber, H.; Lappan, U.; Al-Hussein, M.; Stamm, M.; Voit, B.; Kiriy, A.
(See online at https://doi.org/10.1039/c6py00055j) - High Conductivity in Molecularly p-Doped Diketopyrrolopyrrole-Based Polymer: The Impact of a High Dopant Strength and Good Structural Order. Adv. Mater. 2016, 28, 6003–6010
Karpov, Y.; Erdmann, T.; Raguzin, I.; Al‐Hussein, M.; Binner, M.; Lappan, U.; Stamm, M.; Gerasimov, K.; Beryozkina, T.; Bakulev, V.; Anokhin, D. V.; Ivanov, D. A.; Günther, F.; Gemming, S.; Seifert, G.; Voit, B.; Di Pietro, R.; Kiriy, A.
(See online at https://doi.org/10.1002/adma.201506295) - The impact of molecular weight, air exposure and molecular doping on the charge transport properties and electronic defects in dithienyldiketopyrrolopyrrolethieno[3,2-b]thiophene copolymers. J. Mater. Chem. C 2016, 4, 10827
Di Pietro, R.; Erdmann, T.; Tang, N.; Liu, X.; Gräfe, D.; Lenz, J.; Brandt, J.; Kasemann, D.; Leo, K.; Al-Hussein, M.; Gerasimov, K. L.; Doblas, D.; Ivanov, D. A.; Voit, B.; Neher, D.; Kiriy, A.
(See online at https://doi.org/10.1039/c6tc03545k) - Molecular Doping of a High Mobility Diketopyrrolopyrrole−Dithienylthieno[3,2‐b]thiophene Donor−Acceptor Copolymer with F6TCNNQ. Macromolecules 2017, 50, 914−926
Karpov, Y.; Erdmann, T.; Stamm, M.; Lappan, U.; Guskova, O.; Malanin, M.; Raguzin, I.; Beryozkina, T.; Bakulev, V.; Gunther, F.; Gemming, S.; Seifert, G.; Hambsch, M.; Mannsfeld, S.; Voit, B.; Kiriy, A.
(See online at https://doi.org/10.1021/acs.macromol.6b02452) - Hexacyano-[3]-radialene anion-radical salts: a promising family of highly soluble p-dopants. Chemical Communications 2018, 54, 307–310
Karpov, Y.; Kiriy, N. Mahmoud Al-Hussein; Hambsch, M. ; Beryozkina, T. ; Bakulev, V. ; Mannsfeld, S. C. B. ; Voit, B. ; Kiriy, A.
(See online at https://doi.org/10.1039/c7cc08671g) - Remarkable Mechanochromism in Blends of a π-Conjugated Polymer P3TEOT: The Role of Conformational Transitions and Aggregation. Adv. Optical Mater. 2019, 1901410
Zessin, J.; Schnepf, M.; Oertel, U.; Beryozkina, T.; König, T.; Fery, A.; Mertig, M; Kiriy, A.
(See online at https://doi.org/10.1002/adom.201901410) - AB- versus AA plus BB-suzuki polycondensation: A palladium/tris(tert-butyl)phosphine catalyst can outperform conventional catalysts. Macromol. Rapid Comm. 2020, 41, 1900521
Zhang, K. ; Tkachov, R. ; Ditte, K. ; Kiriy, N. ; Kiriy, A. ; Voit, B.
(See online at https://doi.org/10.1002/marc.201900521) - Ultrasoft and High-Mobility Block Copolymers for Skin-Compatible Electronics. Adv. Mater. 2020, 2005416
Ditte, K.; Perez, J.; Chae, S.; Hambsch, M.; Al-Hussein, M.; Komber, H.; Formanek, P.; Mannsfeld, S. C. B.; Fery, A.; Kiriy, A.; Lissel, F.
(See online at https://doi.org/10.1002/adma.202005416)
