Manipulating photochemical reactivity through restricted bond rotations

通过限制键旋转操纵光化学反应性

• 批准号: 1811795
• 负责人: Jayaraman Sivaguru
• 金额: $ 23.96万
• 依托单位: Bowling Green State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-08-16 至 2020-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1811795&HistoricalAwards=false
• 关键词: Manipulating; photochemical; reactivity; through; restricted

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.

通过该奖项，化学结构、动力学和机理- b项目将支持北达科他州立大学Jayaraman Sivaguru教授的基础研究。Sivaguru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向手性转移到点手性的一般策略。利用键旋转受限的atrosom异构手性发色团，对其光化学和光物理进行了详细的研究。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。这些研究将有助于发展一种连贯的方法，以获得对光引发反应中分子相互作用的基本理解。Sivaguru教授将通过PICNICS（父母与孩子的参与，培养科学中的求知欲）计划整合研究和教育部分。野餐计划是一个面向法戈-摩尔黑德地区高中生的拓展计划，让他们接触研究，并有望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在博士学习期间加强他们的智力科学伙伴关系提供了一个很好的培训途径。该研究项目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。提出的研究旨在通过评估光引发反应中具有atrosom异构发色团的系统中的手性能转移来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，预计将观察到激发态反应的新方面。该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非手性非atrosom异构系统进行比较。

项目成果

Chemoselective Photoreaction of Enamides: Divergent Reactivity towards [3+2]‐Photocycloaddition vs Paternò–Büchi Reaction †

烯酰胺的化学选择性光反应：[3 2] 的不同反应性 – 光环加成与 Paternà – Büchi 反应 –

• DOI: 10.1111/php.13489
• 发表时间: 2021
• 期刊: Photochemistry and Photobiology
• 影响因子: 3.3
• 作者: Kandappa, Sunil Kumar;Kumarasamy, Elango;Singathi, Ravichandranath;Valloli, Lakshmy Kannadi;Ugrinov, Angel;Sivaguru, Jayaraman
• 通讯作者: Sivaguru, Jayaraman