Explorations in crystal engineering

Abstract

Explorations in crystal engineering : supramolecular templates, Explorations in crystal engineering : supramolecular templates, helical assemblies, pharmaceutical reactivity, and applications to helical assemblies, pharmaceutical reactivity, and applications to radio-imaging radio-imaging ____________________________________________ Michael Schultzii To Krista and Jasmine, Sasha, Tayla, Kenzie, and my loving parents iii I do not know what I may appear to the world, but to myself I seem to have been only like a boy playing on the sea-shore, and diverting myself in now and then finding a smoother pebble or a prettier shell than ordinary, whilst the great ocean of truth lay all undiscovered before me. Isaac Newtoniv ACKNOWLEDGEMENTSThere are a number of people I owe my success to, and I would like to take this space to offer them the most sincere love and gratitude for all the things they've done for me. Above all I must thank my research advisor, Professor Leonard R. MacGillivray. He has been a constant source of guidance in navigating the trials of earning a graduate degree. His mentoring has helped me hone my skills as a scientist and, looking back over the past six years, I can hardly believe how much my approach to research and problem solving has changed thanks to his influence. My gratitude to him is never-ending and I will continue to build on the foundation he has helped me establish as I continue in my career. Of course, I must thank the members of the MacGillivray research group, past and present: Beth, and Celymar. The insight, collaboration, and companionship they provided over the years will be some of the fondest memories from my time at Iowa. Also, I would like to thank the undergrads that worked with me, Roxie, Shawna, Kyle, Carlson, and Jeremy, who assisted me in my dissertation work. I am indebted to Dr. Dale Swenson for the enumerable times I bugged him in his office for help with crystallography. Dale never turned me away when I needed help working on a structure or needed advice on how to present and justify less-than-perfect quality data. I owe my knowledge and skill in X-ray crystallography to him and his generous teaching mentality. vi ABSTRACT Crystal engineering is a rapidly developing area of research with goals aimed at designing molecular solids with desired physical and chemical properties. By utilizing reliable intermolecular interactions, the principles of supramolecular chemistry are exploited in the solid state in order to achieve favorable arrangements of molecules in a crystal lattice. We have applied crystal engineering strategies to further develop the strategy of template-directed reactivity in the solid state. An evaluation of catechol, a regioisomer of the commonly used resorcinol template, was performed. Co-crystallization of the template candidate with a bis-pyridyl olefin produced a discrete self-assembled architecture wherein hydrogen-bonded dimers of catechol pre-organize the olefins for a[2+2] photodimerization in the solid state. The dimerization was determined to pro...