Structurally Diverse Molecular Architectures with Unusual Excited State Dynamics and Reactivity Providing Multifunctional Interactions with DNA

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The interaction of inorganic complexes, e.g., cis-platin, with DNA constitutes a major entry point into modulating the reactivity and molecular biology of this critical biomolecule. In this project funded by the Chemical Structure, Dynamics and Mechanism Program, Prof. Karen Brewer will design, prepare and study a group of structurally diverse inorganic complexes which undergo multiple reaction pathways with DNA, using a large array of sensitive methods. A series of new structural motifs with multifunctional reactivity will be prepared to expand the structural diversity of known molecules and create a large class of supermolecules for which each sub-unit modulates some property or performs some function that leads to molecular machines with very complex functions. Understanding and controlling the role of each sub-unit on the properties and reactivity of these unusual multifunctional molecules will be undertaken, including unusual systems that are excited with low energy red light. The project will explore the multifaceted reactivity of these systems including thermal binding to DNA, visible light-induced DNA photobinding via new mechanisms, red light activated DNA photocleavage, and a new paradigm for DNA modification, DNA photocondensation.The discovery of new materials which modulate the activity of DNA has many applications in medicine, including the treatment of genetic and infectious diseases. In addition, the knowledge base assembled by the development of such complex molecules with multiple reaction pathways is applicable in many fields, including the modification and detection of biomolecules, molecular sensing, light and redox activated molecular electronics, conversion of light energy to chemical energy and metal based catalysis.