Manipulating photochemical reactivity through restricted bond rotations

通过这一奖项，化学结构、动力学和机制-B项目将支持北达科他州州立大学法戈分校的贾亚拉曼·西瓦卢教授的基础研究。西瓦卢教授正在开发一种在紫外线和/或可见光引发的化学反应中将轴手性转移到点手性的一般策略。通过使用具有限制键旋转的阿托品手性发色团，将详细研究光化学和光物理。拟议研究的结果将为控制激发态化学提供途径，补充现有的热方法。这些研究将使开发一种连贯的方法来从根本上了解光引发反应中的分子相互作用。西瓦卢教授将通过野餐(家长与孩子的参与，培养对科学的好奇心)计划，将研究和教育部分整合在一起。野餐计划是为法戈-穆尔黑德地区的高中生提供的一个外展计划，让他们接触研究，预计将对他们在本科学习中选择的职业道路产生长期影响。研究和外展活动为研究生提供了一个极好的培训途径，以加强他们在博士学习期间的智力科学伙伴关系。该研究计划的成果将对与光科学和不对称光化学相关的基本概念产生重大影响，并将广泛影响其他领域，如合成化学、纳米科学和材料科学。该研究旨在通过评估光引发反应中具有阿托异构体发色团的体系中的手性能量转移，建立对激发态过程的全面认识和理解。通过在这些发色团中建立的分子限制，预计将观察到激发态反应性的新方面。这项研究将探索具有限制键旋转的系统，以了解新的动力学方面，以及如何利用它们来控制由紫外线和/或可见光引发的激发态反应性，并将它们的光反应性与相应的无手性非阿托异构体系统进行比较。

With this award, the Chemical Structure, Dynamics and Mechanism-B program is supporting the fundamental research of Professor Jayaraman Sivaguru at North Dakota State University, Fargo, ND. Professor Sivaguru is developing a general strategy for transferring axial chirality to point chirality during chemical reactions initiated by UV and/or visible light. By using atropisomeric chiral chromophores that feature restricted bond rotations, the photochemistry and photophysics will be investigated in detail. The outcome from the proposed studies will provide avenues to control excited state chemistry which complement existing thermal methodologies. These studies will enable the development of a coherent approach to gain fundamental understanding of molecular interactions in light initiated reactions. Professor Sivaguru will integrate the research and educational components through the PICNICS (Parents Involvement with Children, Nurturing Intellectual Curiosity in Science) program. The PICNICS program is an outreach program for high school students in the Fargo-Moorhead area that exposes them to research and is expected to have a long-term impact on the career path they take in their undergraduate studies. The research and outreach activities provide an excellent training avenue for graduate students to enhance their intellectual scientific partnership during their doctoral studies. The outcome of the research program will have a significant impact on the basic concepts related to photoscience and asymmetric photochemistry and will broadly influence other fields such as synthetic chemistry, nanoscience and materials science.The proposed research is aimed at building a comprehensive knowledge and understanding of excited state processes by evaluating chiral energy transfer in systems featuring atropisomeric chromophores during light initiated reactions. Through molecular restriction built within these chromophores, it is anticipated that new aspects of excited state reactivity will be observed. The investigation will explore systems featuring restricted bond rotations to understand new dynamic aspects and how they can be harnessed to control excited state reactivity initiated by UV and/or visible light and compare their photo-reactivity with the corresponding achiral non-atropisomeric systems.