Grant: Discovery Grants Program - Individual

This discovery grant program builds on the significant momentum that my award-winning research and training have gained over the past funding cycle. It includes a calculated balance of risk/reward, including relatively low-risk elements suitable for junior trainees that will greatly enhance the understanding of the relationship between structure, bonding, and properties in main group materials chemistry. It also includes higher-risk endeavors suitable for senior trainees that have the potential to redefine the way the community thinks about materials synthesis and design and to produce the next great `wonder' materials. The proposed program is an ideal platform for training, and the funds requested will allow for the creation of 6 graduate and 3 undergraduate training positions that will be occupied by a large number of trainees for the duration of the five-year funding period (a similar plan created 32 BSc, 12 MSc, 8 PhD, and 3 postdoctoral training opportunities during the previous funding cycle). The proposed research will build on our track record of translating fundamental discoveries through to application and leverage the unique chemistries associated with multiple bonds between group 15 elements. It includes built-in outlets for project expansion and additional HQP training involving our large network of academic and industry-based collaborators. Specifically, we will explore research in the following areas: Theme 1: Redox- and Photo-active Lewis Acids/Super Acids - We will take our signature research area in a completely new direction by exploring the chemistry of very strong Lewis acids (i.e., Lewis super acids). We will leverage the unique photo- and redox-active characteristics of formazanate ligands to prepare the target materials and explore their photophysical and redox properties before evaluating them in a variety of applications, including: 1) As (co)initiators for the cationic polymerization of isobutylene. 2) As polymeric sensors for small molecules. 3) As catalysts for organic transformation such as the hydrosilylation of ketones and hydrogenation of imines, including enantioselective routes. Theme 2: Molecular and Macromolecular Materials from Phosphadiazonium Cations - In an effort to transform phosphorus-nitrogen triple bonds from an observable curiosity in outer space to a useful synthon for the production of previously unobtainable materials, we will explore the materials chemistry of phosphadiazonium cations in three different areas. 1) To prepare phosphaformazanate dyes and explore their photophysical and redox properties. 2) To transfer P=N ligands to main group Lewis acids to explore the fundamental coordination chemistry and properties of P=N. 3) As sources of P=N for the exploration of [PN]n chemistry in the bulk and as coatings formed in solution and as a gas phase precursor for ALD. The envisioned materials are expected to have high strength and both anticorrosion and flame-retardant characteristics.