CAREER: Elucidating Structural and Physical Factors that Govern the Temperature Dependence of the Redox Potential in Molecular Compounds

In this CAREER project, Professor Agnes Thorarinsdottir of the Department of Chemistry at the University of Rochester is developing transition metal coordination compounds with highly temperature-sensitive electrochemical properties. Thermoelectric devices are important for the advanced manufacturing of instruments for energy generation, cooling and heating, wearable electronics, and healthcare. The fundamental knowledge gained from this project will enable a transformative approach to the design of next-generation thermoelectric devices that can convert waste heat into electricity for immediate or later use and employ electricity for cooling applications, as well as electrochemical temperature sensors that can operate continuously in remote locations. The goal of this research is to exploit the well-defined structures and synthetic modularity of transition metal complexes to elucidate design principles for molecular compounds that display electrochemical properties that are highly sensitive to temperature changes. Beyond the technical contributions that lie at the interface of inorganic chemistry, materials chemistry, and electrochemistry, the project integrates an educational plan that seeks to educate students and the general public on topics in energy and electrochemistry pertinent to everyday activities and engage students across multiple training stages in hands-on scientific research. These educational efforts will be accomplished through a combination of in-person and online educational activities, including videos, forums, games, workshops, and research opportunities for students, thereby reaching a broad audience of scientists, non-scientists, and students at all levels. Gaining fundamental understanding of factors that govern the temperature sensitivity of the electrochemical potential of molecular compounds is critical to enable the realization of next-generation thermoelectric devices and electrochemical temperature sensors. This project will harness coordination chemistry to rationally design transition metal complexes with highly temperature-sensitive electrochemical potentials, with the goal of understanding how to maximize entropic changes during electron-transfer reactions through synthetic design. This work will establish the impact of chemical structure and physical properties on the temperature dependence of electrochemical behavior. Specifically, the influence of the type, coordination number, and coordination environment of the redox-active transition metal center, electronic metal–metal and metal–ligand interactions, and overall charge of the complex on the temperature sensitivity of electrochemical potential will be investigated. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria. NSF Award ID: 2542274 | Program: 01002627DB NSF RESEARCH & RELATED ACTIVIT | Principal Investigator: Agnes Thorarinsdottir | Institution: University of Rochester, ROCHESTER, NY | Award Amount: $800,000 View on NSF Award Search: https://www.nsf.gov/awardsearch/show-award/?AWD_ID=2542274 View on Research.gov: https://www.research.gov/awardapi-service/v1/awards/2542274.html