The research activities focus on using small molecules to serve as templates to carefully position organic molecules in crystalline solids allowing for better control and improved properties of solid-state materials that undergo chemical reactions. With this technique, important new molecules can be generated directly in the solid state without the need for harmful solvents or expensive catalysts. New generations of "smart materials" will be prepared in this study for use in applications such as sensors, memory devices, and optical switches. The research will integrate underrepresented groups with ongoing efforts to recruit minorities, and the group will continue to develop three undergraduate laboratory experiments at the University of Iowa. As part of these activities, the project leader will host the Midwest Organic Solid State Chemistry Symposium (MOSSCS) and will introduce a website that has the undergraduate experiments. Active collaborations between the Iowa group and visiting faculty at three undergraduate colleges in the Midwest are ongoing. The project lead is also working with the Superintendent, Assistant Superintendent, and Science Coordinator of the Iowa City Community School District to develop a program that opens the eyes of high-school students to careers as scientists. The program will involve viewings of the critically acclaimed documentary Naturally Obsessed and a mini-TED talk by the project leader on organic solid-state chemistry.
The general goal of this project is to apply small-molecule and dinuclear metal-organic templates to address fundamental problems and challenges that confront chemists to organize molecules to react in the organic solid state. With support from the Solid State and Materials Chemistry program in the Division of Materials Research, the project will apply templates to organic solids by determining: (i) a general ability of templates to direct intramolecular photodimerizations, (ii) a general ability of templates to direct multiple stacks of aromatics with olefins that photodimerize to give both dimers and oligomers, and (iii) the ability of a template to support two reactions in a solid in the form of a photodimerization and photochromism. The research is motivated by the fact that although templates are rapidly emerging as tools to control reactivity in solids, highly-promising and fundamentally important avenues of needed investigation remain unaddressed. When the research is completed, we expect that it will be possible to more broadly apply reactions in solids to problems of organic synthesis (e.g. unusual architectures), green chemistry (e.g. solvent-free preparation), inorganic chemistry (e.g. porosity), and materials science (e.g. multifunctional solids). Specifically, the research team expects to generalize the use of dinuclear Ag(I) complexes to direct intramolecular photodimerizations of a 1,8-bis(4-pyridyl)naphthyl diene. Intramolecular cyclizations that afford complex unsymmetrical [2.2]cyclophanes and ladderanes will be studied. In a second aim, indolocarbazoles will be employed as templates that direct stacks of more than two olefins. Templates will be used to generate both dimers and difficult-to-achieve oligomers. In a final aim, the team will develop a template derived from resorcinol and salicylidene functionalities that both directs a [2+2] photodimerization and supports an intermolecular proton transfer and isomerization that leads to photochromism. The approach to engineer two reactions will take advantage of the modularity of the template method that enables ready integration of organic functionality in solids.
