EAGER: Exploring Radical Anions as Catalysts in Conjugated Polymer Synthesis

在这个由化学催化计划和化学系的大分子、超分子和纳米化学计划资助的项目中，密歇根大学的Anne McNeil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，它们的许多性质来自于链之间的纠缠和相互作用。聚合物已经成为我们日常生活中无处不在的材料，影响到大多数行业，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，但有一种被称为共轭聚合物的子集可以导电，并已被用作聚光太阳能电池和发光显示器的活性元件。麦克尼尔教授将研究将分子连接在一起形成共轭聚合物的新化学方法。据估计，到2017年，导电聚合物市场将增长到16亿美元，因此开发这种聚合方法的潜在影响是巨大的。更广泛的影响还包括培训本科生和研究生，指导在化学科学中代表性较低的少数群体的本科生，以及通过在会议和期刊上发表演讲来广泛传播研究成果。合成共轭聚合物的链式聚合方法仍然局限于少数富含电子的单体。在这个项目中，麦克尼尔教授正在研究自由基阴离子催化，以链生长的方式合成共轭的、电子缺乏的聚合物。人们正在开发和研究基于自由基阴离子机制的目标化合物齐聚反应的模型系统，目的是了解和控制引发和传播化学。使用反应性研究、电子顺磁共振波谱、质谱学的动力学和机理分析相结合的方法被应用于深入了解这些体系的化学组成，然后将这些知识转化为聚合方法。这些研究应该会对该领域产生重大影响，因为具有特定组成、序列、长度和分散性的给体/受体共聚物将首次可用。

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.