LEAPS-MPS: Fluorous Photocatalysts for the Activation of Organic Compounds

LEAPS-MPS：用于活化有机化合物的氟光催化剂

• 批准号: 2316906
• 负责人: Lorenzo Mosca
• 金额: $ 24.97万
• 依托单位: University of Rhode Island
• 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: 2023-09-01 至 2025-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2316906&HistoricalAwards=false
• 关键词: LEAPS; MPS; Fluorous; Photocatalysts; Activation

In this project, co-funded by the Directorate for Mathematical and Physical Sciences (MPS) and the Established Program to Stimulate Competitive Research (EPSCoR), and managed by the Chemistry Division, Professor Lorenzo Mosca and his students at the University of Rhode Island will perform studies to advance the applications of organic photocatalysts in functional group transformations and C–H bond activation of organic substrates. Efficient and robust photocatalysts will be needed to perform chemical transformations in greener, more economical ways. Such photocatalysts will be both resistant to photodegradation and amenable to easy recovery and purification. Professor Mosca and his students will design and synthesize fluorous photocatalysts with absorption spanning the visible and near-UV visible wavelength ranges, study the photophysical and electrochemical performance thereof in both fluorous and non-fluorous environments, and demonstrate their successful application in organic transformations. This research will generate new insights into the design of robust and recyclable photocatalysts for more efficient organic syntheses. Prof. Mosca and his students will perform outreach and provide mentorship to students in regional high schools serving underrepresented groups from urban and suburban neighborhoods, with a focus on engagement of the students with STEM disciplines and on improving retention rates in lower-level college classes. Professor Mosca and his research group will prepare and study fluorous organic photocatalysts with the goal of improving their resistance to photodegradation and photobleaching, increasing recovery of the intact photocatalyst from reaction mixtures, and lengthening the usable lifespan of the photocatalyst. Comprehensive photophysical and electrochemical characterization of the prepared photocatalysts will inform the design of successive generations of photocatalysts, enabling selective organic transformations. These studies will constitute a critical step in pursuing the selective tuning of catalytic activity in fluorous and non-fluorous phases, whereby competing reaction pathways can be enhanced or suppressed by using different reaction environments. Two commonly competing reaction pathways for an organic compound are photoredox reactions, involving reduction or oxidation of the substrate, and atom transfer reactions with no net charge generation, each with different reaction product outcomes. Prof. Mosca and his students will demonstrate the use of fluorous photocatalysts for the tuning of organic functional group transformations as well as C–H bond activation reactions by leveraging the properties of fluorous phases alone or in combination with traditional organic and aqueous phases.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.

在这个由数学和物理科学理事会（MPS）和刺激竞争研究的既定计划（EPSCoR）共同资助，并由化学部门管理的项目中，罗得岛大学的Lorenzo莫斯卡教授和他的学生将进行研究，以推进有机光催化剂在有机基质的官能团转化和C-H键活化中的应用。将需要高效和强大的光催化剂以更绿色，更经济的方式进行化学转化。这样的光催化剂将既耐光降解又易于回收和纯化。莫斯卡教授和他的学生将设计和合成吸收跨越可见光和近紫外可见光波长范围的氟光催化剂，研究其在氟和非氟环境中的物理和电化学性能，并展示其在有机转化中的成功应用。这项研究将为设计更有效的有机合成的耐用和可回收的光催化剂提供新的见解。莫斯卡教授和他的学生将进行外展，并提供辅导，以学生在区域高中服务来自城市和郊区社区代表性不足的群体，重点是学生与干学科的参与，并提高在较低水平的大学班级的保留率。莫斯卡教授和他的研究小组将制备和研究氟有机光催化剂，目的是提高其抗光降解和光漂白的能力，增加反应混合物中完整光催化剂的回收率，并延长光催化剂的使用寿命。所制备的光催化剂的综合物理和电化学表征将为连续几代光催化剂的设计提供信息，从而实现选择性有机转化。这些研究将构成一个关键的步骤，在追求选择性调整的催化活性，在氟和非氟相，从而竞争的反应途径可以通过使用不同的反应环境得到增强或抑制。有机化合物的两种常见的竞争反应途径是光氧化还原反应，涉及底物的还原或氧化，以及不产生净电荷的原子转移反应，每种反应具有不同的反应产物结果。莫斯卡教授和他的学生将演示使用氟光催化剂调节有机官能团的转换以及C-通过单独利用氟相或与传统有机相和水相结合利用氟相的性质进行H键活化反应。该奖项反映了NSF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进行评估，被认为值得支持的搜索.