Manipulating photochemical reactivity through restricted bond rotations

有了这个奖项，化学结构，动力学和机制-B计划是支持教授Jayaraman Sivaguru在北达科他州州立大学，法戈，ND的基础研究。Sivaguru教授正在开发一种通用策略，用于在紫外线和/或可见光引发的化学反应期间将轴向手性转移到点手性。通过使用阻转异构手性发色团的功能限制键旋转，光化学和光物理将被详细研究。拟议研究的结果将提供控制激发态化学的途径，补充现有的热方法。这些研究将使一个连贯的方法，以获得光引发的反应中的分子相互作用的基本理解的发展。西瓦古鲁教授将通过PICNICS（家长参与儿童，培养科学知识）计划整合研究和教育部分。PICNICS计划是为法戈-穆尔黑德地区的高中生提供的一项外展计划，该计划使他们接触到研究，预计将对他们在本科学习中的职业道路产生长期影响。研究和推广活动为研究生提供了一个很好的培训途径，以加强他们在博士学习期间的知识科学伙伴关系。该研究计划的成果将对光科学和不对称光化学的基本概念产生重大影响，并将广泛影响合成化学、纳米科学和材料科学等其他领域。拟议的研究旨在通过评估光引发反应过程中具有阻转异构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。通过在这些发色团内建立的分子限制，预期将观察到激发态反应性的新方面。该调查将探索具有限制键旋转的系统，以了解新的动态方面，以及如何利用它们来控制由UV和/或可见光引发的激发态反应性，并将其光反应性与相应的非手性非阻转异构系统进行比较。

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.