Manipulating photochemical reactivity through restricted bond rotations

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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.