Template-Controlled Synthesis: Covalent Bond Formation Made Easy in the Solid State Leonard R. MacGillivray, University

1. Template-Controlled Synthesis: Covalent Bond Formation Made Easy in the Solid State Leonard R. MacGillivray, University of Iowa,DMR-0133138 Scientific Merit: The MacGillivray group is developing a general method to form covalent bonds in the organic solid state. Whereas synthetic organic chemistry is reliably conducted in solution, such reliability, owing to effects of close packing, has not been generally realized in the solid state. Specifically, in this CAREER award, molecular templates are used to preorganize olefins for [2+2] photodimerizations. The group has shown that the reaction can be controlled using either hydrogen-bond or coordination-driven self-assembly (J. Am. Chem. Soc.2004, 126, 9158; Angew. Chem., Int. Ed. 2005, 44, 3569) (right) and can be used to construct complex molecules (e.g. molecular ladders). Figure 1. Use of Zn(II) and Ag(I) ions within templates that direct [2+2] photodimerizations in the solid state.

2. Template-Controlled Synthesis: Covalent Bond Formation Made Easy in the Solid State Leonard R. MacGillivray, University of Iowa,DMR-0133138 Who: Professor Leonard R. MacGillivray Where: Department of Chemistry, University of Iowa What: Research laboratory is developing a general method to control chemical reactivity in the organic solid state. So What?: The organic solid state is an untapped medium for systematically controlling chemical reactivity. The solid state differs from the liquid phase (i.e. where chemists ‘normally’ conduct synthetic chemistry) in that the solid state offers a solvent-free environment and can provide access to molecules that cannot be obtained in the liquid phase. Controlling reactivity in the solid state can also lead to the development of unique devices for applications in ultra-high density data storage.

3. Template-Controlled Synthesis: A New Undergraduate Laboratory and a Working Weekend Leonard R. MacGillivray, University of Iowa,DMR-0133138 Immediate Relevance, Education and Outreach: The MacGilliray group has developed a sophomore undergraduate laboratory that involves the template method (J. Chem. Ed., in press). In particular, approximately 350 undergraduates have been introduced to the fields of solid-state, supramolecular, and green chemistry by performing a template-controlled solid-state organic synthesis. In addition to the undergraduate laboratory, the group has used results from the CAREER Award to develop a ‘Working Weekend’ tutorial that teaches undergraduate students from regional colleges in Iowa, Illinois, Missouri, and Wisconsin how to collect, solve, and refine single-crystal X-ray structure data. Figure 2. Snapshots from X-ray crystallography tutorial developed at the University of Iowa.

4. Template-Controlled Synthesis: Covalent Bond Formation Made Easy in the Solid State Leonard R. MacGillivray, University of Iowa,DMR-0133138 Who: Professor Leonard R. MacGillivray Where: Department of Chemistry, University of Iowa What: Research laboratory is developing a general method to control chemical reactivity in the organic solid state. So What?: Being an untapped medium, it is not surprising that undergraduate students remain largely unaware of the benefits of synthetic chemistry in the organic solid state. The MacGillivray group aims to break down this barrier by targeting ways to incorporate organic solid-state synthesis into undergraduate curricula and settings.