Organogels from Diketopyrrolopyrrole Copolymer Ionene/Polythiophene Blends Exhibit Ground-State Single Electron Transfer in the Solid State

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Stegerer, Dominik ; Pracht, Martin ; Guenther, Florian ; Sun, Hengda ; Preis, Kevin ; Zerson, Mario ; Maftuhin, Wafa ; Tan, Wen Liang ; Kroon, Renee ; McNeill, Christopher R. ; Fabiano, Simone ; Walter, Michael ; Biskup, Till ; Gemming, Sibylle ; Magerle, Robert ; Mueller, Christian ; Sommer, Michael

• Tipo de documento: Artigo Científico
• Fonte: MACROMOLECULES; v. 55, n. 12, p. 16-pg., 2022-06-08.

Resumo

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(g(4)2T-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(g(4)2T-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. (AU)

• Processo FAPESP: 18/15670-5 - Novos materiais semicondutores baseadas em PDMS e DPP para Eletrônicas Flexíveis e Esticáveis: Fabricação, Análise e Aplicações em Dispositivos Orgânicos
• Beneficiário: Florian Steffen Günther
• Modalidade de apoio: Bolsas no Brasil - Pós-Doutorado