This award to University of Iowa by the Solid State Materials Chemistry program in the Division of Materials Research is to incorporate organic groups into templated reactions, which are carried out using organic solid state photochemistry. Major goal is to develop methods to incorporate small (e.g. vinyl) and large (e.g. t-butyl) groups, as well as carboxylic acids into the templated reactions, and to construct decorated targets such as cyclophanes and ladderanes. Other aims of the project are to exploit and elaborate to direct these photoreactions using organic templates to make: a) tunable changes in fluorescence emission; and b) non-covalent functionalization of metal-organic polyhedra via anion exchange. This project represents a first attempt to systematically integrate organic functionalities into a dependable method to control bimolecular reactivity in the crystalline state. Success of this project can lead to the designed, solvent-free synthesis of complex molecules and materials with tunable properties. In addition, structure-property relationships developed in this project could also be applied to additional solid-state reactions.
The proposed educational activities will involve integration of the proposed research activities into the undergraduate curriculum by developing an inorganic laboratory experiment course that focuses upon single-crystal-to-single-crystal transformations. As part of outreach educational activities, ?Working Weekends? workshops on X-ray crystallography and powder diffraction will be expanded to include both lectures and experiments. This outreach activity will be extended via cyberinfrastructure and through the development of a mobile X-ray unit. A published organic laboratory experiment, as well as a new inorganic experiment course will be disseminated electronically to students and faculty members of the local area colleges via the internet on the educational website. This website is being further developed by the PI to make it available for laboratory experiments in supramolecular chemistry.
Intellectual Merit Research in the MacGillivray group focuses upon controlling the properties of solid-state materials. Solids surround us in the form of electronics, pharmaceutics, and absorbents. The focus of the current project was to control chemical reactions in organic solids. By controlling chemical reactivity, we expect to be able to improve the properties of solids (e.g. timed drug release). In particular, we aimed to increase the range of molecules that undergo reactions in solids. From our project, our findings demonstrate that we are able to increase the breadth of molecules that undergo reaction. We also discovered that molecules are able to undergo unusual dynamic movements, which suggest that organic solids may be developed to behave as switching devices. Our findings also revealed that we can form our reactive solids without use of organic solvents through the use of mortar-pestle-grinding and undergo catalysis. Broader Relevance We translated our research into undergraduate education by developing two undergraduate laboratory experiments that directly implement our ideas to control reactivity in the solid state. Being able to eliminate solvent in the design of organic solids has implications for creating and sustaining a cleaner environment. The knowledge that we gained can also be transferred to other disciplines within chemistry (e.g. organic synthesis) and affect commercial processes (e.g. catalysis).
