Expanding the Scope and Enabling Potential of Direct Arylation Polymerization (DArP)

化学部的大分子、超分子和纳米化学项目支持Barry C. Thompson教授的项目。汤普森教授是南加州大学化学系的一名教员。汤普森教授的研究开发了新的合成方法来制备共轭聚合物。共轭聚合物已经成为有机电子器件的一个极具吸引力的平台，特别是用于太阳能电池和发光二极管等应用。目前制造这些装置的合成方法很困难。这些反应通常需要高活性和易燃的试剂来制备。这些普遍的化学反应也将单体的类型限制在一个狭窄的组，进一步限制了聚合物性能的范围。本研究描述了一种开发新的合成技术的策略，用于制造聚合物，直接芳基化聚合（DArP），成为一个强大的，广泛的，并且能够合成共轭聚合物的平台。汤普森教授?他的假设是，通过仔细控制反应参数和添加剂，可以使DArP与各种单体体系广泛兼容，并且可以比传统的共轭聚合物合成方法表现出更好的选择性。该研究项目还为共轭聚合物合成提供了一条更加绿色和可持续的途径。该研究通过南加州大学-喜瑞都学院暑期实习项目为社区大学生提供培训。DArP的优化和由DArP生产的聚合物的最终规模扩大为太阳能电池应用的聚合物合成提供了一种更经济、更环保的方法。这项研究描述了汤普森教授？将直接芳基化聚合（DArP）发展成为一个强大的、影响广泛的、能够合成共轭聚合物的平台。这项工作的动机是基于有限的方法，共轭聚合物的合成。虽然DArP可以很好地绕过金属化要求，但目前它在官能团耐受性和缺陷最小化方面落后于最先进的方法，如Stille方法，在控制聚合物生长方面落后于Kumada催化转移缩聚（KTCP）反应。因此，这项工作的主要目标是：1。建立一个广泛适用的直接芳基化聚合平台，既通用又稳健；2 .发展氧化直接芳基化聚合，制备无需单体预活化的聚合物；完善DArP平台，以增强对聚合物生长的控制和与更丰富的金属催化剂的相容性。汤普森教授?实现这些目标的方法是基于小分子直接芳基化的有希望的观察结果的假设驱动研究。这种方法不仅能够扩展小分子化学，而且能够通过简单的、模块化的反应参数控制来适应和开发新的聚合物化学。

The Macromolecular, Supramolecular and Nanochemistry Program of the Chemistry Division supports the project by Professor Barry C. Thompson. Professor Thompson is a faculty member in the Department of Chemistry at the University of Southern California (USC). Professor Thompson's research develops new synthetic methods to prepare conjugated polymers. Conjugated polymers have emerged as a highly attractive platform for organic electronics and specifically for applications such as solar cells and light emitting diodes. The current synthetic methods of making these devices are difficult. These reactions typically require highly reactive and flammable reagents for preparation. These prevailing chemistries also limit the type of monomers to a narrow group, further limiting the range of polymer properties. This research describes a strategy to develop the new synthetic technique for making polymers, Direct Arylation Polymerization (DArP), into a robust, broad-reaching, and enabling platform for the synthesis of conjugated polymers. Professor Thompson?s hypothesis is that through careful control of reaction parameters and additives, DArP can be made to be broadly compatible with a variety of monomer systems and can exhibit selectivity better than traditional methods of conjugated polymer synthesis. The research project also offers a significantly more green and sustainable route to conjugated polymer synthesis. The research provides training for community college students through the USC-Cerritos College summer internship program. Optimization of DArP and the ultimate scale-up of polymers made by DArP provides a significantly more economical and environmentally friendly way to synthesize polymers for solar cell applications. This research describes Professor Thompson?s strategy to develop Direct Arylation Polymerization (DArP) into a robust, broad-reaching, and enabling platform for the synthesis of conjugated polymers. Motivation for this work is based on the limited methods for conjugated polymer synthesis. While DArP can attractively bypass metalation requirements, it currently lags behind state-of-the-art methods like Stille methods in terms of functional group tolerance and minimization of defects andas Kumada catalyst-transfer polycondensation (KTCP) reactions in terms of control over polymer growth. As a result, the major objectives of this work are to: 1. Establish a broadly applicable direct arylation polymerization platform that is both versatile and robust, 2. Develop oxidative direct arylation polymerization for the generation of polymers without preactivation of the monomers, and 3. Refine the DArP platform for enhanced control over polymer growth and compatibility with more abundant metal catalysts. Professor Thompson?s approach toward achieving these objectives is a hypothesis driven study based on promising observations in small molecule direct arylation. This methods has theability to not just extend small molecule chemistry but to adapt and develop new polymer chemistry through simple, modular control of reaction parameters.