EAGER: Exploring Radical Anions as Catalysts in Conjugated Polymer Synthesis

在这个由化学催化项目和化学学部的大分子、超分子和纳米化学项目资助的项目中，密歇根大学的安妮·麦克尼尔教授正在开发制备共轭聚合物的新方法。聚合物是长链有机分子，其许多特性来自于链之间的缠结和相互作用。聚合物已经成为我们日常生活中无处不在的材料，影响着大多数行业，包括农业和食品，健康和安全，以及交通运输。虽然这些材料中的大多数都是绝缘的，但被称为共轭聚合物的一个子集可以导电，并已被用作光收集太阳能电池和发光显示器的有源组件。麦克尼尔教授将研究将分子连接起来形成共轭聚合物的新化学物质。到2017年，导电聚合物的市场预计将增长到16亿美元，因此开发这种聚合方法的影响可能是巨大的。更广泛的影响还包括培训本科生和研究生，指导来自化学科学领域代表性不足的少数群体的本科生，以及通过在会议上发表报告和在期刊上发表文章广泛传播研究成果。用于合成共轭聚合物的链式生长聚合方法仍然局限于一组狭窄的富电子单体。在这个项目中，麦克尼尔教授正在研究自由基阴离子催化，以链式生长方式合成共轭的缺电子聚合物。为了理解和控制化合物的起始和扩散化学，人们正在开发和研究基于自由基阴离子机制的聚合物模型系统。反应性研究、EPR光谱学、质谱学等动力学和机理分析的结合，正被用于深入了解这些体系的化学性质，然后将这些知识转化为聚合方法。这些研究将对该领域产生重大影响，因为将首次获得具有特定组成、序列、长度和分散度的供体/受体共聚物。

In this project funded by the Chemical Catalysis Program and the Macromolecular, Supramolecular, and Nanochemistry Program of the Chemistry Division, Professor Anne McNeil of the University of Michigan is developing new methods to prepare conjugated polymers. Polymers are long chain organic molecules that derive many of their properties from the entanglements and interactions between the chains. Polymers have become ubiquitous materials in our daily lives, impacting most industries, including agriculture and food, health and safety, as well as transportation. While most of these materials are insulating a subset, known as conjugated polymers, can conduct charge and have been used as active components in light-harvesting solar cells and light-emitting displays. Professor McNeil will study new chemistries to connect molecules together to form conjugated polymers. The market for conducting polymers is estimate to grow to $ 1.6 billion by 2017, so the impact of developing a this polymerization methodology is potentially significant. The broader impacts further involve training undergraduate and graduate students, mentoring undergraduate students from minority groups underrepresented in the chemical sciences, and disseminating research results broadly through presentations at conferences and publications in journals.Chain-growth polymerization methods for synthesizing conjugated polymers remains limited to a narrow set of electron-rich monomers. In this project, Professor McNeil is studying radical anion catalysis to synthesize conjugated, electron deficient polymers in a chain-growth fashion. Model systems for the putative radical anion mechanism-based olgomerization of the subject compounds are being developed and studied with the goal of understanding and controlling the initiation and propagation chemistries. A combination of kinetic and mechanistic analyses using reactivity studies, EPR spectroscopy, mass spectrometry, are being applied to gain insights into the chemistries of these systems and then to convert this knowledge into polymerization methodology. These studies should make a significant impact on the field as donor/acceptor copolymers with specified compositions, sequences, lengths and dispersities will be accessible for the first time.