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

在这个项目中，由数学和物理科学理事会（MPS）和促进竞争研究的既定计划（EPSCoR）共同资助，由化学部门管理，罗德岛大学的Lorenzo Mosca教授和他的学生将进行研究，以推进有机光催化剂在有机底物的官能团转化和C-H键活化中的应用。为了以更环保、更经济的方式进行化学转化，将需要高效、强大的光催化剂。这种光催化剂既耐光降解，又易于回收和纯化。Mosca教授和他的学生将设计和合成具有可见光和近紫外可见光吸收波长范围的含氟光催化剂，研究其在含氟和非含氟环境下的光物理和电化学性能，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坚固和可回收的光催化剂提供新的见解。Mosca教授和他的学生将为来自城市和郊区社区的代表性不足的地区高中的学生提供外展和指导，重点是让学生参与STEM学科，并提高低水平大学课程的保留率。Mosca教授及其研究小组将制备和研究含氟有机光催化剂，目的是提高其抗光降解和光漂白能力，提高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。对所制备的光催化剂进行全面的光物理和电化学表征，将为后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。这些研究将是追求氟相和非氟相催化活性选择性调整的关键一步，从而通过使用不同的反应环境来增强或抑制竞争反应途径。有机化合物的两种相互竞争的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，每种反应都有不同的反应产物结果。Mosca教授和他的学生将展示使用含氟光催化剂来调节有机官能团转化以及C-H键激活反应，通过利用氟相单独或与传统有机相和水相结合的性质。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。

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.