CAS: Electrochemical and Photochemical Methods for Precision Synthesis of Conjugated Polymers

CAS：精密合成共轭聚合物的电化学和光化学方法

• 批准号: 2305056
• 负责人: Nathan Romero
• 金额: $ 49.5万
• 依托单位: University of California-San Diego
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-07-01 至 2026-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2305056&HistoricalAwards=false
• 关键词: CAS; Electrochemical; Photochemical; Methods; Precision

With the support of the Macromolecular, Supramolecular and Nanochemistry program in the Division of Chemistry, Nathan Romero of the University of California at San Diego is developing electrochemical and photochemical methods for precision synthesis of conjugated polymers. Conjugated polymers carry significant potential for applications as organic electronic materials owing to their lightweight, flexible nature and diverse optoelectronic properties. However, realization of advanced technologies necessitates a degree of structural control beyond current synthetic capabilities. This work addresses this limitation and will seek to achieve length- and sequence-controlled polymerization of conjugated polymers using a combination of electrochemical and photochemical tools to polymerize a broad range of simple arene substrates. The developed methodology will be applied to the synthesis of novel polymers for organic electronics and new methods for additive manufacturing. The synthetic innovations associated with this research have the potential to create advanced organic electronic devices with applications in sustainable energy, healthcare, and communications. Furthermore, the designed photochemical reactivity of monomers may be applicable to the upcycling of conjugated polymers once used rather than discard these as waste. The interdisciplinary nature of this research will provide educational and professional development opportunities for student researchers. The research team will work to increase representation of non-majority scholars through inclusive mentoring, teaching and service. Outreach activities to local communities will focus on educational resources related to electronic waste handling and disposal, sustainable polymer feedstocks and biodegradable plastics.This research will focus on developing the length- and sequence-controlled polymerization of thiophene based monomers using a combination of electrochemical and photochemical tools. The modular platform for precision synthesis of conjugated polymers will utilize electrochemical C-H functionalization to selectively couple an arene and a sulfide to form an arylsulfonium salt, which will also serve as monomer in a novel photo-mediated chain growth polymerization. By performing electrolysis and photolysis simultaneously, the sulfide will essentially act as a catalyst to achieve controlled oxidative polymerization. The developed direct method for the preparation of arylsulfonium salts through C-H functionalization aims to improve upon the atom economy of existing multi-step chemical methods. The photopolymerization studies have the potential to provide fundamental knowledge on the photochemical reactivity of conjugated polymers and introduce conceptually novel mechanisms for controlling molecular weight through wavelength modulation. Strategies that reduce the reliance on transition metals for polymerizing aromatic units are important for improving the sustainability of polymer science and technology. In general terms, this research has the potential to provide a more universal approach to sequence-defined and controlled polymerizations of conjugated polymers.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.

在化学系高分子、超分子和纳米化学项目的支持下，加州大学圣地亚哥分校的 Nathan Romero 正在开发用于精确合成共轭聚合物的电化学和光化学方法。 共轭聚合物由于其轻质、柔性和多样化的光电特性，在有机电子材料方面具有巨大的应用潜力。然而，先进技术的实现需要超出当前合成能力的一定程度的结构控制。 这项工作解决了这一限制，并将寻求使用电化学和光化学工具的组合来聚合各种简单的芳烃底物，从而实现共轭聚合物的长度和序列控制聚合。开发的方法将应用于有机电子新型聚合物的合成和增材制造的新方法。与这项研究相关的合成创新有可能创造出先进的有机电子设备，并应用于可持续能源、医疗保健和通信领域。此外，设计的单体光化学反应性可适用于共轭聚合物的升级循环，而不是将其作为废物丢弃。这项研究的跨学科性质将为学生研究人员提供教育和专业发展机会。研究团队将致力于通过包容性的指导、教学和服务来增加非多数学者的代表性。 当地社区的外展活动将重点关注与电子废物处理和处置、可持续聚合物原料和可生物降解塑料相关的教育资源。这项研究将重点开发利用电化学和光化学相结合的噻吩基单体的长度和序列控制聚合工具。 用于精确合成共轭聚合物的模块化平台将利用电化学C-H官能化选择性地偶联芳烃和硫化物以形成芳基锍盐，该盐也将用作新型光介导链增长聚合中的单体。通过同时进行电解和光解，硫化物本质上将充当催化剂以实现受控的氧化聚合。 所开发的通过C-H官能化制备芳基锍盐的直接方法旨在提高现有多步化学方法的原子经济性。光聚合研究有可能提供有关共轭聚合物光化学反应性的基础知识，并引入通过波长调制控制分子量的概念性新颖机制。减少芳香族单元聚合对过渡金属的依赖的策略对于提高聚合物科学和技术的可持续性非常重要。总的来说，这项研究有潜力为共轭聚合物的序列定义和受控聚合提供更通用的方法。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查进行评估，被认为值得支持标准。