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.

在化学系大分子、超分子和纳米化学项目的支持下，肯尼索州立大学的Graham Collier教授正在开发一种合成共轭单体的新方法，这种方法将参与多种聚合策略，并获得不同类别的半导体可回收聚合物。半导体聚合物是一种有机大分子，其中一个主链的交替单键和多键导致π共轭。这使得分子轨道重叠，从而允许电子的离域。在掺杂过程之后，离域电子可以自由移动，当它们通过共轭聚合物主链时产生电流。目前，共轭聚合物是最重要的一类塑料，用于光电子器件，如移动设备和计算机中的LED屏幕，太阳能电池，储能，传感器等。然而，许多满足这些应用性能指标的共轭体系具有复杂的结构，需要多个合成步骤，并且在聚合过程中产生有毒废物。这项工作解决了这些问题，并将重点放在用较少的合成步骤从市售的醛、苯胺和其他生物基起始材料合成共轭单体上。此外，合成将在空气中进行，不需要大量的净化。聚合也将绕过通常需要的低温空气和无水条件。除了对单体设计对聚合物性能影响的基本见解之外，还将制备可降解/可回收的共聚物。通过这项研究，共轭聚合物合成的进步将通过减少对化石燃料资源的需求和采用更低能源密集型的加工方法，广泛地支持能源安全。该项目将为研究生和本科生提供高分子合成和大分子表征技术方面的培训。实验室研究将辅以高年级有机/高分子课程，使学生熟悉大分子科学、学术研究的基本概念，以及这些概念如何与社会问题联系起来。协同研究和教育倡议将为代表性不足的群体，特别是非洲裔美国人、妇女和来自北乔治亚农村的第一代学生提供机会。本研究将侧重于开发模块化、简单、高效的富电子吡咯合成方法，用于新型和可定制的共轭聚合物。在第一个阶段，将制备二卤代吡咯[3,2-b]吡咯（H2DPP），并使用直接杂芳基化聚合将其结合到共轭聚合物的主链中。重点将放在基本的设计和结构-性质的关系，如光学，电化学和热性质。第二个重点将集中在合成可降解和可回收的基于h2dpp的共轭共聚物上。这将通过酸催化双醛H2DPP与各种二胺的阶梯生长共聚来实现。这种策略将消除对过渡金属催化剂的需求。更重要的是，聚合物主链中产生的亚甲基官能团可以很容易地被酸降解成它们各自的单体。这项工作的结果有可能为新的单体构建模块提供基础信息，为有机电子领域的可持续发展方法开发简单的聚合物，并证明H2DPPs在氧化还原活性应用中的可行性。所设计的工艺具有高原子经济性，能源效率高，比目前使用的方法更环保。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

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.