CAS: Modular, Simple, and Efficient Synthesis of Electron-Rich Pyrrolopyrroles for Novel and Tailorable Conjugated Polymers

CAS：模块化、简单、高效地合成富电子吡咯并吡咯，用于新型、可定制的共轭聚合物

• 批准号: 2203340
• 负责人: Graham Collier
• 金额: $ 39.51万
• 依托单位: Kennesaw State University Research and Service Foundation
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-06-01 至 2025-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2203340&HistoricalAwards=false
• 关键词: CAS; Modular; Simple; Efficient; Synthesis

With the support of the Macromolecular, Supramolecular and Nanochemistry program in the Division of Chemistry, Professor Graham Collier of Kennesaw State University is developing a new approach for synthesizing conjugated monomers that will participate in numerous polymerization strategies and access a diverse class of semiconducting recyclable polymers. Semiconducting polymers are organic macromolecules in which a backbone of alternating single and multiple bonds results in pi-conjugation. This enables overlapping of molecular orbitals, which in turn allows for the delocalization of electrons. Following the doping process, the delocalized electrons become free to move around, resulting in an electrical current as they pass along the conjugated polymer backbone. Currently, conjugated polymers are the most important class of plastics used for optoelectronic devices such as LED screens in mobile devices and computers, solar cells, energy storage, sensors, and many others. However, many of the conjugated systems that meet performance metrics for these applications have complex structures, require multiple synthetic steps and generate toxic waste during polymerization protocols. This work addresses these issues and will focus on the synthesis of conjugated monomers in fewer synthetic steps from commercially available aldehydes, anilines and other biobased starting materials. Furthermore, the synthesis will be performed in the air and will not require extensive purification. The polymerization will also bypass commonly required cryogenic air- and water-free conditions. Beyond fundamental insights into the influence of monomer design on the polymer properties, degradable/recyclable copolymers also will be prepared. The advances in the synthesis of conjugated polymers that will be enabled by this research broadly support energy security by lessening demand on fossil fuel resources and employing less energy-intensive processing methods. This project will provide graduate and undergraduate students with training in polymer synthesis and macromolecular characterization techniques. Laboratory research will be complimented by efforts to develop upper division organic/polymer curriculum that will enable students to become familiar with fundamental concepts of macromolecular science, academic research, and how these are connected to societal problems. Synergistic research and education initiatives will provide opportunities for under-represented groups, especially African Americans, women, and first-generation students from rural North Georgia.This research will focus on the development of modular, simple, and efficient synthesis of electron-rich pyrrolopyrroles for novel and tailorable conjugated polymers. In the first thrust, dihalogenated pyrrolo[3,2-b]pyrroles (H2DPP) will be prepared and incorporated into the main chain of conjugated polymers using direct heteroarylation polymerization. A strong focus will be placed on fundamental design and structure-property relationships such as optical, electrochemical, and thermal properties. The second thrust will center on the synthesis of degradable and recyclable H2DPP-based conjugated copolymers. This will be achieved by acid-catalyzed step-growth copolymerization of dialdehyde H2DPP with various diamines. Such strategy will eliminate the need for transition metal catalysts. More importantly, the resulting azomethine functional groups in the polymer backbone can readily be degraded by acid to their respective monomers. Outcomes from this work have the potential to provide fundamental information regarding new monomeric building blocks, develop simple polymers for sustainable approaches in organic electronics, and demonstrate the viability of H2DPPs in redox-active applications. The designed processes have high atom economy, are energy efficient and more environmentally benign than currently utilized methodologies.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.

在化学系中的大分子，超分子和纳米化学计划的支持下，肯尼索州立大学的格雷厄姆·科利尔教授正在开发一种新的方法，用于合成共轭单体，以参与许多聚合策略，并访问多样化的循环可恢复可循环可循环的可裂解聚合物。 半导体聚合物是有机大分子，其中单键和多个键的骨架会导致PI结合。 这使得分子轨道重叠，这又允许电子的脱位。 在掺杂过程之后，离域电子变得自由移动，从而导致电流沿共轭聚合物主链传递。 当前，共轭聚合物是用于光电设备的最重要类别的塑料类别，例如移动设备和计算机，太阳能电池，储能，传感器等中的LED屏幕。 但是，许多满足这些应用程序性能指标的共轭系统具有复杂的结构，需要多个合成步骤并在聚合协议期间产生有毒废物。 这项工作解决了这些问题，并将重点关注共轭单体的合成，从市售醛，苯胺和其他基于生物的起始材料中的合成步骤较少。 此外，该合成将在空中进行，不需要广泛的纯化。 聚合还将绕过通常需要的低温空气和无水的条件。 除了对单体设计对聚合物性能的影响的基本见解外，还将准备降解/可回收共聚物。 这项研究将通过减少对化石燃料资源的需求并采用较少能源密集型加工方法来广泛支持能源安全的共同聚合物的合成进步。 该项目将为研究生和本科生提供聚合物合成和大分子特征技术的培训。实验室研究将通过开发上层有机/聚合物课程的努力来称赞，这将使学生能够熟悉大分子科学，学术研究的基本概念，以及这些概念与社会问题如何相关。 协同研究和教育计划将为代表性不足的群体，尤其是来自佐治亚州农村农村农村的非裔美国人，妇女和第一代学生提供机会。这项研究将集中于开发针对电子富含电子的吡咯吡咯并有效地合成针对新颖和可定制的可构成的，可定制的和可定制的吡咯吡咯的合成。 在第一个推力中，使用直接杂化聚合物的主链制备并将其掺入主链中，并使用直接的杂化聚合物融合到主链中。 将重点放在基本设计和结构 - 特性关系上，例如光学，电化学和热性能。 第二个推力将集中在可降解和可回收H2PPP的共轭共聚物的合成中。 这将通过酸催化的二醛H2DPP与各种二胺共聚的循环生长共聚。 这种策略将消除过渡金属催化剂的需求。更重要的是，聚合物主链中产生的唑吡啶官能团可以通过酸轻松地将其各自的单体降解。 这项工作的结果有可能提供有关新单体构建块的基本信息，为有机电子中的可持续方法开发简单的聚合物，并证明H2DPP在氧化还原活性应用中的生存能力。 该设计的过程具有高原子经济性，能节能效率高，并且比目前使用的方法学更加良性。该奖项反映了NSF的法定任务，并且使用基金会的知识分子优点和更广泛的影响评估标准，被认为值得通过评估来获得支持。

项目成果

Azomethine‐Containing Pyrrolo[3,2‐ b ]pyrrole Copolymers for Simple and Degradable Conjugated Polymers

甲亚胺—含吡咯并[3,2—b]吡咯共聚物的简单且可降解的共轭聚合物

• DOI: 10.1002/marc.202300220
• 发表时间: 2023
• 期刊: Macromolecular Rapid Communications
• 影响因子: 4.6
• 作者: Bartlett, Kimberley A.;Charland‐Martin, Ariane;Lawton, Jonathan;Tomlinson, Aimée L.;Collier, Graham S.
• 通讯作者: Collier, Graham S.