Advancing the Performance and Capabilities of Direct Arylation Polymerization (DArP)

化学系的大分子、超分子和纳米化学项目获得该奖项，资助南加州大学的Barry C.Thompson博士开发绿色、节能的方法来生产半导体聚合物。这种现有的塑料-电子材料在有机太阳能电池和发光二极管以及将光转换为电流的几种传感应用中显示出巨大的前景。在这项工作中，半导体聚合物是用基于廉价和丰富的元素如铜和镍的催化剂制备的。这些金属被用来降低与聚合过程相关的能量障碍，使原始材料更容易转化为所需的产品。因此，它们的使用提高了半导体聚合物的可持续性，并使聚合物具有新的反应性和性能。与该奖项相关的新工艺提供了沿着主聚合链以几种不同方式组装重复单体单元的方法，不仅产生了由相同重复单元组成的直线链，而且还产生了这些重复单元不同且以受控和可预测的方式排列的链。因此，在这些聚合物中使用这种先进的体系结构可以改善它们的应用，特别是它们将阳光转化为电能的效率。这项工作使本科生和研究生能够在聚合物化学方面获得出色的培训，并从Cerritos社区学院扩展到南加州大学的学生。通过与德国慕尼黑路德维希·马克西米利安大学开展研究生交换项目产生的广泛影响，对于帮助学生接触更广泛的国际研究和合作非常重要。本研究致力于开发以铜和镍配合物为催化剂的直接芳基化聚合的替代合成路线，以合成共轭半导体聚合物。还特别强调使用绿色和环境友好的溶剂。直接芳基化聚合的能力通过专注于从逐级增长过渡到链增长来扩展，这使得能够获得更先进的体系结构，如嵌段和梯度共聚物。有关直接芳基化聚合实现可控活性聚合的研究是该领域研究的重要进展，因为它将使控制分子量和聚合物多分散性成为可能。另一个方向涉及为相关的脱氢聚合过程探索更可持续的氧化剂，以避免单体卤化和使用化学计量比的银氧化剂。通过这项工作使用富含地球的铜和镍催化剂来获得共轭聚合物是重要的，并有可能显著降低现有共轭聚合物合成程序的成本和复杂性，这些程序通常不是原子效率高的，需要苛刻的反应条件，有毒溶剂，并产生大量废物。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With this award, the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry is funding Dr. Barry C. Thompson from the University of Southern California to develop green and energy efficient methods to produce semiconducting polymers. This existing class of plastic-electronic materials has shown great promise for use in organic solar cells and light emitting diodes, as well as several sensory applications in which light is converted to electrical current. In this work, semiconducting polymers are prepared using catalysts based on inexpensive and abundant elements such as copper and nickel. These metals are utilized to lower the energy barrier associated with polymerization processes, making it easier to convert starting materials to desired products. Consequently, their use improves the sustainability of semiconducting polymers and enables new reactivity and properties in the polymers. The new processes associated with this award provide means to assemble the repeating monomer units along main polymer chains in several different ways giving rise not only to linear chains composed of identical repeating units, but also chains in which those repeating units are different and arranged in controlled and predictable ways. Consequently, access to such advanced architectures in these polymers could lead to improvements in their applications, specifically the efficiency by which they convert sunlight into electricity. The work enables outstanding training for undergraduate and graduate students in polymer chemistry, extending to students hosted at the University of Southern California from Cerritos Community College. The broad impact through the development of a graduate student exchange program with Ludwig Maximillians University in Munich, Germany is very important for helping to expose students to the broader scope of international research and collaboration. This research is focused on the development of alternative synthetic routes to direct arylation polymerization catalyzed by copper and nickel complexes for the synthesis of conjugated, semiconducting polymers. Special emphasis is also placed on the use of green and environmentally friendly solvents. The capabilities of direct arylation polymerization are extended by focusing toward a transition from step-growth to chain-growth, which enables access to more advanced architectures such as block and gradient copolymers. Studies related to the ability of direct arylation polymerization to effect controlled living polymerization are a significant step forward in this area of research because it would enable control over the molecular weight and polymer polydispersity. An additional direction involves exploration of more sustainable oxidants for the related dehydrogenative polymerization process that avoids monomer halogenation and the use of stoichiometric amounts of silver oxidants. The use of earth-abundant copper and nickel catalysts to access conjugated polymers via this work is important and has the potential to significantly reduce the cost and complexity of existing procedures for conjugated polymer synthesis, which are generally not atom efficient, require harsh reaction conditions, toxic solvents, and create significant amounts of waste products.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.