Coordination Chemistry and Non-Innocent Behavior of Nitrosoarene-Pyridine/Polypyridine Hybrid Ligands

This project concerns the synthesis, spectroscopic studies and theoretical calculations of ruthenium and osmium complexes containing multidentate nitrosoarene-pyridine/ polypyridine hybrid ligands. Very recently, our group reported a series of ruthenium complexes bearing nitrosoarene with pyridyl chelate. Detailed structural, electrochemical, spectroscopic and theoretical studies on these complexes suggested that nitrosoarene-pyridine hybrid ligands are attractive alternatives to polypyridines in the development of inorganic luminophores and sensitizers. On the other hand, nitrosoarene has recently been pointed out to be a class of non-innocent ligand which has been largely overlooked in the literature. In this proposal, we plan to develop a general synthetic route for metal complexes bearing multidentate nitrosoarenepyridine/ polypyridine hybrid ligands. We will then perform detailed spectroscopic and theoretical investigations in order to understand the metal-[nitrosoarene-pyridine/ polypyridine] bonding interaction in different metal or ligand oxidation states, and study the photophysical/photochemical properties associated with the complexes. These studies should provide fundamental understanding on metal-nitrosoarene bonding interaction and insight on designing functional transition metal complexes.