With funding from the Macromolecular, Supramolecular, and Nanochemistry Program of the Chemistry Division, Professor Kyle N. Plunkett of Southern Illinois University at Carbondale is creating new supramolecular assemblies based on organic cyclic molecules that contain the chemical element iodine. Inspired by nature, supramolecular chemistry utilizes hydrogen bonding to dictate assemblies such as proteins, enzymes, and DNA. In this research, general strategies are developed to prepare building blocks for assemblies based on amino acids containing iodine fragments. These building blocks provide a framework for 3D structures that have applications in gas/molecular absorption and sensing. The bonding and properties are investigated using several experimental techniques. This project contributes to the training of a diverse group of students. The research team is designing 180-degree 3D videos of laboratory experiments and demonstrations. The video content is used with virtual reality headsets to immerse internet-connected learners in a virtual chemistry world. Outreach activities focus on recruitment of local high school students to participate in research stays over the summer, winter or spring breaks.
This research is focused on developing new supramolecular assemblies based on hypervalent iodine macrocycles that are synthesized from amino acid functionalized benziodazoles. These molecules self-assemble through secondary bonding into macrocyclic structures, which are the building block for the higher order supramolecular structures including molecular cages and covalent organic frameworks. These macrostructures provide a framework to build molecular cages by linkages made through non-natural amino acid side chains. Specific goals of this work are to explore the dynamic covalent bonding of hypervalent iodine macrocycles and identify expedient synthetic routes towards molecular cages. The investigators also seek to quantify guest ion/molecule binding affinity, reaction-promoted disassembly and solid-state properties and characterize covalent organic frameworks based on hypervalent iodine macrocyclization reactions. This research provides new methods to guide supramolecular assemblies, which is of fundamental interest because of the new bonding and reactivity possibilities that could provide access to properties such as chiral recognition and reactivity. Additionally, potential impacts of this research include the design and synthesis of high surface area materials that have emerging properties for applications in gas/molecule absorption and sensing.
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.
