Molecular Electrochemistry as Enabling Technology in Inorganic and Bioinorganic Chemistry

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As was dramatically shown by the award of the 2019 Nobel Prize in Chemistry for the development of lithium-ion batteries (Li-ion), basic research on the most prosaic topics can have world altering outcomes. There are many different Li-ion battery types, but all depend on a knowledge of the intercalation of ions into layered transition-metal oxides and sulfides, topics that were studied for decades before the application to reliable light-weight rechargeable batteries was conceived. A major theme of the proposed research involves the intimate details of the chemistry of sulfur-nitrogen rich molecules. There is certainly a link to another major technology for energy storage, namely the sodium-sulfur battery (regarding behaviour of the trisulfur radical anion S3- in such batteries). However, the more likely future application of this proposal is to miniaturized sensors and detectors for molecular electronics. Another major theme of this research proposal relates to the chemical synthesis of highly reactive organophosphorus compounds. These will be used to develop new chemical compounds with the rare metal ruthenium and testing their biological activity in cells, which have the potential to replace ageing platinum-based chemotherapies to which cancers have developed increased immunity. The original work on platinum compounds came entirely unexpectedly from the use of supposedly inert platinum electrodes to study the effects of electric fields on bacteria. An overarching theme of this proposal is the use of molecular electrochemistry as an enabling technology to guide chemical synthesis, provide mechanistic insights into the basic processes involved in, and induced by, electron-transfer (or `redox') reactions. The work proposed here often requires environments far-removed from daily life. Work is done in inert-atmosphere chambers of various kinds. Structures are measured at the molecular level using high-energy X-ray diffraction. Electrical work employs specialized circuitry that provides high degrees of control on the applied voltages and on the accurate measurement of small currents. Spectroscopy is further used to analyze matter by its interactions with varying frequencies of electromagnetic radiation. Magnetic resonance spectroscopy uses radio or microwave frequencies on samples held in homogeneous magnetic environments. All these techniques require sophisticated installations of multi-user instrumentation. Finally, in alignment with my training philosophy most of the requested funding goes to provide modest stipends for young HQP who are augmenting their BSc education by several years of full- time research experience, which ultimately has many returns to the Canadian economy. Further increases in fundamental research funding will improve the remuneration of these young people who are being trained to be productive members of the knowledge society.