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.

中文翻译：

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来自二酮吡咯并吡咯共聚物紫罗烯/聚噻吩共混物的有机凝胶表现出固态的基态单电子转移

具有低最低未占分子轨道 (LUMO) 能级的受体共聚物是有机电子学的关键材料。在目前的工作中，吡啶侧翼二酮吡咯并吡咯 (PyDPPPy) 的季铵化用于将所得单体 (MePyDPPPy) 的 LUMO 能级降低多达 0.7 eV。即使在过量的三甲基氧鎓四氟硼酸盐中，MePyDPPPy 急剧变化的电子特性也会阻碍第二个甲基化步骤，从而可以实现 N-杂环侧翼 DPP 结构单元的不对称功能化。相应的以二噻吩为共聚单体的n型聚合紫罗烯PMePyDPPPyT2与p型聚噻吩P(g ₄2T-TT)，表明这对共聚物之间的特定交叉相互作用。其他 p 型/n 型聚合物对不存在的聚合物共混溶液的凝胶化对于将不同的电子聚合物同时（共）加工和取向成薄膜或细丝具有普遍意义。_{详细的光学和电子表征表明，由有机凝胶加工而成的薄膜表现出基态电子转移 (GSET)，这是通过适当定位的最高占据分子轨道 (HOMO) 和 P(g 4} 2T-TT) (-4.07 eV)的 LUMO 能级和PMePyDPPPyT2 (-4.20 eV)，分别。此外，与凝胶化和 GSET 相关的分子相互作用似乎不会显着影响聚合物共混膜的形态。