Synergistic catalysis for the sustainable synthesis of semiconducting polymers

近年来，半导体聚合物在有机电子领域的广泛应用引起了人们的兴趣，包括有机发光二极管（oled）、有机场效应晶体管（ofet）、有机光伏（opv），以及最近在生物领域的应用。这些材料在性能上取得的进步很大程度上可以归因于越来越复杂的聚合物的合成，这些聚合物可能成本高，耗时长，并且对环境不可持续。在这一提议中，我们研究了使用交叉脱氢偶联（CDC）聚合来提高合成效率。一年来，我们取得了以下主要成就：扩大了可用于CDC聚合的单体范围。发现了与四氟苯配对的一个新的给体单体（呋喃）和与噻吩配对的一个新的受体（二氟苯并噻唑）。发展供体-受体（DA单体）以促进向活性聚合的过渡。除了原子经济性外，将D-A半导体聚合物合成过程中的时间和能量投入最小化是提高D-A半导体聚合物生产的环境友好性和可扩展性的重要组成部分。根据我们之前的结果，随着链的延伸，可以观察到速率的提高，我们假设da型单体的合成会导致更快的聚合。数据表明，与D单体和a单体的聚合相比，da型单体的聚合速率加快了5倍。

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.