Organogels from Diketopyrrolopyrrole Copolymer Ionene/Polythiophene Blends Exhibit Ground-State Single Electron Transfer in the Solid State
Journal article, 2022
Acceptor copolymers with low lowest unoccupied molecular orbital (LUMO) energy levels are key materials for organic electronics. In the present work, quaternization of pyridine-flanked diketopyrrolopyrrole (PyDPPPy) is used to lower the LUMO energy level of the resulting monomer (MePyDPPPy) by as much as 0.7 eV. The drastically changed electronic properties of MePyDPPPy hinder a second methylation step even in an excess of trimethyloxonium tetrafluoroborate and thereby give access to the asymmetric functionalization of N-heterocycle-flanked DPP building blocks. The corresponding n-type polymeric ionene PMePyDPPPyT2 with bithiophene as comonomer forms thixotropic organogels with the p-type polythiophene P(g42T-TT), indicative of specific cross-interactions between this couple of copolymers. Gelation of polymer blend solutions, which is absent for other couples of p-type/ n-type polymers, is of general interest for (co)processing and orientation of different electronic polymers simultaneously into films or filaments. Detailed optical and electronic characterization reveals that films processed from organogels exhibit ground-state electron transfer (GSET) enabled by suitably positioned highest occupied molecular orbital (HOMO) and LUMO energy levels of P(g42T-TT) (-4.07 eV) and PMePyDPPPyT2 (-4.20 eV), respectively. Furthermore, molecular interactions related to gelation and GSET do not appear to significantly influence the morphology of the polymer blend films.
Author
Dominik Stegerer
Chalmers, Chemistry and Chemical Engineering, Applied Chemistry
Technische Universität Chemnitz
Martin Pracht
Technische Universität Chemnitz
Florian Günther
University of Sao Paulo (USP)
Hengda Sun
Linköping University
Kevin Preis
Technische Universität Chemnitz
Mario Zerson
Technische Universität Chemnitz
Wafa Maftuhin
University of Freiburg
Wen Liang Tan
Monash University
Renee Kroon
Linköping University
Chalmers, Chemistry and Chemical Engineering, Applied Chemistry
Christopher R. McNeill
Monash University
S. Fabiano
Linköping University
Michael Walter
University of Freiburg
Till Biskup
Universität des Saarlandes
Sibylle Gemming
Technische Universität Chemnitz
Robert Magerle
Technische Universität Chemnitz
Christian Müller
Chalmers, Chemistry and Chemical Engineering, Applied Chemistry
M. Sommer
Technische Universität Chemnitz
Macromolecules
00249297 (ISSN) 15205835 (eISSN)
Vol. 55 12 4979-4994Double Doping of Semiconducting Polymers
Swedish Research Council (VR) (2018-03824), 2018-01-01 -- 2021-12-31.
Subject Categories
Polymer Chemistry
Materials Chemistry
Condensed Matter Physics
DOI
10.1021/acs.macromol.2c00655