Synergistic catalysis for the sustainable synthesis of semiconducting polymers

近年来，半导体聚合物在有机电子学的广泛应用中引起了极大的兴趣，包括有机发光二极管（OLED）、有机场效应晶体管（OFFET）、有机光致发光器件（OPV），以及最近在生物学应用中。这些材料在性能方面取得的进步在很大程度上可以归功于合成更复杂的聚合物，这可能是昂贵的，耗时的，环境不可持续的。在这个建议中，我们已经研究了使用交叉偶联（CDC）聚合，以提高合成的效率。过去一年的主要成就如下：1。扩大了可用于CDC聚合的单体范围。发现了一种新的与四氟苯配对的给体单体（呋喃）和一种新的与噻吩配对的受体（二氟苯并噻二唑）.开发供体-受体（DA单体），以促进向实现活性聚合的过渡。除了原子经济性之外，在D-A半导体聚合物的合成过程中最小化时间和能量输入是改善D-A半导体聚合物生产的环境友好性和可扩展性的重要部分。基于我们先前的结果，即观察到随着链的延伸速率提高，合成DA型单体，假设这些单体将导致更快速的聚合。数据显示，与D单体和A单体的聚合相比，DA型单体导致5倍的速率加速。

In recent years, semiconducting polymers have attracted much interest in a wide range of applications in organic electronics, including organic light emitting diodes (OLEDs), organic field-effect transistors (OFETs), organic photovoltaics (OPVs), and more recently, in biological applications. The advances made in performance of these materials can largely be attributed to the synthesis of ever more complex polymers, which can be costly, time-consuming, and environmentally unsustainable. In this proposal, we have investigated the use of cross-dehydrogenative coupling (CDC) polymerizations to improve the efficacy of the synthesis. Key achievements this past year are the following:1. Expansion of monomer scope that can be used in the CDC polymerization. One new donor monomer (furan) paired with tetrafluorobenzene and one new acceptor (difluorobenzothiadiazole) paired with thiophene have been identified.2. Development of donor-acceptor (DA monomers) to facilitate the transition towards achieving a living polymerization. In addition to atom economy, minimizing time and energy input in the synthetic process of D-A semiconducting polymers is an essential part of improving the environmental friendliness and scalability of D-A semiconducting polymer production. Based on our prior results that a rate enhancement was observed as the chain extended, DA-type monomers were synthesized hypothesizing that these would lead to more rapid polymerizations. The data show that the DA-type monomer leads to a rate acceleration of 5x compared to the polymerization of a D monomer and an A monomer.