Transition metal photosensitizers have been a prominent topic due to their importance in photovoltaic cells, solar fuel production, and photoredox catalysis. Currently available technology relies heavily on the use of precious metals, which limits the potential for large-scale applications due to the low abundance and high cost of the metal precursors. Earth abundant zirconium was chosen as a low-cost alternative to precious metals because cyclopentadienyl zirconium chalcogenolates have been reported to exhibit photoluminescent properties. However, these complexes lack the ability to undergo reversible electrochemical processes, which is a required property for solar energy conversion. Inspired by previous studies, we are trying to develop zirconium complexes with a mixed ligand system of cyclopentadienyl (Cp) and a redox non-innocent ligand, such as catecholate or benzenedithiolate. We hypothesized that the combination of these ligands that can undergo reversible electron transfer and photoluminescent complexes would result in compounds with favorable optical and electrochemical properties for applications in solar energy conversion or photoredox chemistry. Despite several different synthetic strategies, our attempts to prepare Cp<sub>2</sub>Zr catecholate were unsuccessful due to uncontrolled pathways leading to complex product mixtures. The synthesis of Cp<sub>2</sub>Zr benzenedithiolate has proven to be clean and easy to handle, and studies of its photophysical and electrochemical properties are currently underway.

Revisiting zirconocene complexes for use as molecular photosensitizers

255th National Meeting (2018)

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