Research Summary

Our research program revolves around three main projects that target the synthesis and use of fused heterocyclic stable carbocation that can act as Lewis acidic ligands for metal complexes, photocatalysts for bond formation and cleavage, or electrolyte for redox flow batteries that can be used as energy storage.

Members of the group will receive rigorous training in air-sensitive organometallic synthesis, and in solid-state synthetic methods, along with homogeneous and heterogeneous catalysis. A broad range of physical methods including single crystal and powder X-ray diffraction, transmission electron microscopy, multinuclear NMR, UV/vis, IR, EPR, and X-ray absorption spectroscopy, as well as cyclic voltammetry will be used to characterize new complexes and materials.

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Carbocation containing ligands

Project 1: The incorporation of Lewis acid moieties within ligands, so-called ambiphilic ligands, has recently been shown to possess unusual coordination properties and to have a strong impact on metal reactivity, inducing unique chemical behavior. So far, Lewis acid-assisted reactivity has been limited mostly to stoichiometric transformations and only a handful of ligand systems exist. The goal of this project is to synthesize complexes containing transition metal – carbocation Z-type interactions. The nature of this novel transition metal – Lewis acid (TM – LA) interaction will be studied and used to perform stoichiometric and catalytic hydrogenation, C-H activation, and X atom transfer.

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Red-light-mediated transformation

Project 2: Over the past decade, photoredox catalysis has rapidly developed and caught tremendous attention from synthetic chemists. Iridium and ruthenium polypyridyl complexes are among the most widely used and effective photo-redox catalysts (PCs). Yet their high cost, low sustainability, and potential toxicity are significant drawbacks. Organic dyes have been proven to be efficient alternatives, however, these can suffer from narrow redox window, pH-dependent. All widely used PCs are limited by the use of high energy light source. The goal of our project is to develop organic PCs that can be easily tuned, versatile, and utilized low energy light sources.

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Symmetric Redox Flox Battery

Project 3: Efficient storage of electricity remains one of the greatest challenges faced by the scientific community in the quest for clean energy. Redox-Flow-Batteries (RFBs), in which the energy is stored in liquid electrolyte solutions that flow through a battery of electrochemical cells during charge and discharge, is one of the promising technologies. Organic RFBs are a promising alternative to the expensive metal base batteries. Yet, these suffer from low efficiency and robustness, small open circuit potential (OCV), and cross-contamination. The goal of this project is to develop symmetric RFBs in the electrolyte are stable and photoactive heterocyclic carbenium with large OCV

Thomas L. Gianetti
Assistant Professor
Department of Chemistry and Biochemistry, University of Arizona.
CSML 638, 1306 E. University Blvd., Tucson, AZ 85719
Office: +1 520 626 3609

email: tgianetti@arizona.edu