Chemical, Electrochemical and Physical Properties of Metallosupramolecular Architectures with Tetrazine Based Ligands Including Investigations of Anion-pi Interactions

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In this project funded by the Macromolecular, Supramolecular and Nanochemistry Program of the Chemistry Division, Kim Dunbar of the Texas A&M University will study various aspects of anion-pi interactions: anion interactions with aromatic molecules. The goals are to study metal complexes with ligands containing electropositive tetrazine rings that form unusual molecular ring assemblies including five-membered pentagons exhibiting high stabilities in solution and remarkable flexibility that allows them to be easily converted to other ring sizes by the addition of different anions. Another goal is to study chemical reactions triggered by the capture or release of anions which may be a way to alter the physical and chemical properties of the assemblies. Data from solid-state, solution, gas phase and computational studies will be used to assess the strength of anion-pi forces and to assist in future experiments aimed at predicting structures. One application of this research will be to design very large polyhedral molecules by using the five-membered ring molecules as building blocks. Another application will be to construct molecular magnets by taking advantage of the ease of reduction of tetrazine ligands to prepare organic radicals that can act as bridges between paramagnetic metal ions. The broader impacts of the research include graduate student and postdoctoral researcher training in the chemical sciences, efforts to broaden the participation of underrepresented groups in chemical science research, and outreach to local museums and science fairs in order to enhance scientific and technological understanding. The versatility of skills required to work on the project presents an excellent opportunity for students to learn about a broad spectrum of research disciplines. In this project the assembly of organic molecules and metal ions will be harnessed to promote the formation of large geometric structures that often can display unusual properties useful for applications. This work will expand the repertoire of chemistry that can be used to create magnetic and conducting materials starting with molecular components. The results of these studies could have many important long term impacts on a variety of applications in which magnetic materials are important, including non-volatile memory and spintronics.