Research Initiation Award: Establishing the Fundamentals of Spin-Crossover Behavior and Catalysis in Single-Chain Nanoparticle Metallopolymers

Spelman College, Atlanta GA

Investigators

Abstract

Research Initiation Awards provide support for junior and mid-career faculty at Historically Black Colleges and Universities who are building new research programs or redirecting and rebuilding existing research programs. It is expected that the award helps to further the faculty member's research capability and effectiveness, improve research and teaching at the home institution, and involves undergraduate students in research experiences. Black women are a significantly under-represented group in STEM, and one important way to remedy this is to provide training and research opportunities to Black women early in their academic careers. The research projects proposed here are carried out by undergraduates at Spelman College: Black women who are working to establish themselves in STEM. In addition to providing them with valuable scientific training in the fields of computational science, inorganic chemistry, and polymer chemistry, this research provides them with networking and professional development opportunities as well. This research is focused on using computational chemistry to model and better understand the behavior of certain metal-containing polymers. The results of the research itself can also have significantly beneficial impacts on human society by leading to the design of improved catalysts and new multifunctional materials. One of the overarching goals of polymer science is to develop materials that have the functions and capabilities of proteins but are not limited by their fragility or complex synthesis. A class of materials that can potentially fulfill these criteria are single-chain nanoparticle (SCNP) metallopolymers. It has been found that metal containing SCNPs can act as effective catalysts for numerous reactions, suggesting that they could be potential “artificial enzymes”. Using modern computational chemistry techniques (chiefly density functional theory and QM/MM simulations) the mechanisms of several catalytically active SCNP metallopolymers are being computed to help elucidate the atomistic details of their reaction pathways and how these are influenced by their polymeric features. Spin-state is also known to be an important feature in metalloenzyme reactivity and could also affect the mechanistic and catalytic behavior of SCNP enzyme mimics as well. Therefore, systematic modeling of SCNP model systems is being performed to determine the underlying principles that govern spin-state energetics in SCNP metallopolymers. The goal of this work is to develop molecular design strategies for rationally incorporating spin-crossover (SCO) behavior into SCNPs. By establishing a roadmap for combining the inherently quantum mechanical state-switching properties of SCO with the dynamic and modular behavior of SCNP systems, novel, soft, multifunctional materials with protein-like characteristics can be developed in the future. 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.