CAS: Development of Core-Substituted Dihydrophenazine Photoredox Catalysts for Organocatalyzed Atom Transfer Radical Polymerization

CAS：用于有机催化原子转移自由基聚合的核取代二氢吩嗪光氧化还原催化剂的开发

• 批准号: 2055742
• 负责人: Garret Miyake
• 金额: $ 47.5万
• 依托单位: Colorado State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-06-01 至 2024-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2055742&HistoricalAwards=false
• 关键词: CAS; Development; Core; Substituted; Dihydrophenazine

With the support of the Chemical Catalysis program in the Division of Chemistry, Garret Miyake of Colorado State University is studying a new class of organic catalysts for the synthesis of polymers with precisely defined molecular weights, chemical compositions, and architectures. Polymers are among the most important synthetic materials in modern society. Developing new and efficient methods for their synthesis accelerates the discovery of new materials and applications. Catalysts enable the synthesis of medicines, commodity chemicals, and materials but are often based on precious metals and require elevated reaction temperatures. The expected outcomes from this work are the development of new organic catalysts as sustainable alternatives to commonly used precious metal catalysts that allow access to otherwise unobtainable polymers. Furthermore, these catalysts will convert light to chemical energy to drive reactions under mild conditions. In collaboration with a local high school, the Miyake group is developing supplemental curricula to educate high school students in modern themes of sustainability. High school students are also working with the Miyake research team at Colorado State University to develop these catalyst systems and gain research experience in the diverse skill sets necessary to address global challenges. With the support of the Chemical Catalysis program in the Division of Chemistry, Garret Miyake of Colorado State University is studying core-substituted dihydrophenazine photoredox catalysts for organocatalyzed atom transfer radical polymerization. This work will establish synthetic routes to novel organic photoredox catalysts possessing unique photophysical properties that will enable the synthesis of new polymeric materials. Through mechanistic studies, an understanding into the structure-property relationships of the catalysts on their polymerization performance will be gained to ultimately yield more efficient catalyst systems. These catalysts will be applied toward the polymerization of challenging monomers for the synthesis of novel polymeric materials. Beyond polymerization, these catalysts will also have the potential to unlock previously inaccessible catalytic chemical transformations and will find broad applications across chemical catalysis.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.

在化学系化学催化项目的支持下，科罗拉多州立大学的Garret Miyake正在研究一种新的有机催化剂，用于合成具有精确定义的分子量、化学组成和结构的聚合物。聚合物是现代社会最重要的合成材料之一。开发新的有效的合成方法加速了新材料和新应用的发现。催化剂能够合成药物、商品化学品和材料，但通常以贵金属为基础，需要较高的反应温度。这项工作的预期结果是开发新的有机催化剂，作为通常使用的贵金属催化剂的可持续替代品，这些催化剂允许获得否则无法获得的聚合物。此外，这些催化剂将把光转化为化学能，在温和的条件下驱动反应。与当地一所高中合作，三宅集团正在开发补充课程，以教育高中生现代可持续发展主题。高中生还与科罗拉多州立大学的三宅一生研究团队合作开发这些催化剂系统，并在应对全球挑战所需的各种技能方面获得研究经验。在化学系化学催化项目的支持下，科罗拉多州立大学的Garret Miyake正在研究用于有机催化原子转移自由基聚合的核心取代二氢吩嗪光氧化还原催化剂。这项工作将建立新型有机光氧化还原催化剂的合成路线，这些催化剂具有独特的光物理性质，将使新的聚合物材料的合成成为可能。通过机理研究，了解催化剂的结构-性能关系对其聚合性能的影响，最终得到更有效的催化剂体系。这些催化剂将应用于具有挑战性的单体的聚合，以合成新型聚合物材料。除了聚合，这些催化剂还将有可能解开以前无法实现的催化化学转化，并将在化学催化剂中得到广泛应用。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。

项目成果

Structure–property relationships of core-substituted diaryl dihydrophenazine organic photoredox catalysts and their application in O-ATRP

核取代二芳基二氢吩嗪有机光氧化还原催化剂的结构—性能关系及其在O-ATRP中的应用

• DOI: 10.1039/d1py01060c
• 发表时间: 2021
• 期刊: Polymer Chemistry
• 影响因子: 4.6
• 作者: Price, Mariel J.;Puffer, Katherine O.;Kudisch, Max;Knies, Declan;Miyake, Garret M.
• 通讯作者: Miyake, Garret M.