Moser Maximilian, Savva Achilleas, Thorley Karl, Paulsen Bryan D, Hidalgo Tania Cecilia, Ohayon David, Chen Hu, Giovannitti Alexander, Marks Adam, Gasparini Nicola, Wadsworth Andrew, Rivnay Jonathan, Inal Sahika, McCulloch Iain
University of Oxford, Department of Chemistry, Oxford, OX1 3TA, UK.
King Abdullah University of Science and Technology (KAUST), Biological and Environmental Science and Engineering Division, Thuwal, 23955-6900, Saudi Arabia.
Angew Chem Int Ed Engl. 2021 Mar 29;60(14):7777-7785. doi: 10.1002/anie.202014078. Epub 2021 Feb 26.
Donor-acceptor (D-A) polymers are promising materials for organic electrochemical transistors (OECTs), as they minimize detrimental faradaic side-reactions during OECT operation, yet their steady-state OECT performance still lags far behind their all-donor counterparts. We report three D-A polymers based on the diketopyrrolopyrrole unit that afford OECT performances similar to those of all-donor polymers, hence representing a significant improvement to the previously developed D-A copolymers. In addition to improved OECT performance, DFT simulations of the polymers and their respective hole polarons also reveal a positive correlation between hole polaron delocalization and steady-state OECT performance, providing new insights into the design of OECT materials. Importantly, we demonstrate how polaron delocalization can be tuned directly at the molecular level by selection of the building blocks comprising the polymers' conjugated backbone, thus paving the way for the development of even higher performing OECT polymers.
供体-受体（D-A）聚合物是用于有机电化学晶体管（OECT）的有前景的材料，因为它们在OECT运行期间将有害的法拉第副反应降至最低，然而它们的稳态OECT性能仍远远落后于全供体同类材料。我们报道了三种基于二酮吡咯并吡咯单元的D-A聚合物，其提供了与全供体聚合物相似的OECT性能，因此相对于先前开发的D-A共聚物有显著改进。除了改进的OECT性能外，对这些聚合物及其各自的空穴极化子的密度泛函理论（DFT）模拟还揭示了空穴极化子离域与稳态OECT性能之间的正相关关系，为OECT材料的设计提供了新的见解。重要的是，我们展示了如何通过选择构成聚合物共轭主链的结构单元在分子水平上直接调节极化子离域，从而为开发性能更高的OECT聚合物铺平道路。
