Our group has shown the visible-light photocatalytic application of group IV zirconium with dianionic, pincer-type pyridine dipyrrolide ligand as a candidate for the development of cost-effective photosensitizers. However, this complex inherently lacks oxidative quenching pathways that are common to many precious metal counterparts. This limitation is addressed by using different ligand systems based on their past records: bis-cyclopentadienyl (Cp) for long luminescent lifetime with group IV metals and redox active ligands such as 1,2- dithiolate for prototypical oxidative chemistry in d<sup>0</sup> metal complexes. Preliminary data of (bis-Cp)Zr(dithiolate) reveals excitation in the visible light region and the nature of the electronic transitions is established through DFT calculations. Hafnium and titanium complexes have also been made and identified via X-ray crystallography and NMR spectroscopy. With systematic ligand modification, the optical and electrochemical properties of these metallocenes will also be tested.

Reimagine early transition metal luminescent metallocenes with built-in redox-active ligands

256th National Meeting (2018)

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