Historically, lanthanide chemistry has been dominated by the +3 oxidation state. Lower oxidation state species have recently attracted significant attention, however, due to their potential applications and unique properties. Access to oxidation states below the common +3 have typically required use of forcing conditions and strong chemical reductants, limiting broader utilization and further studies. In this talk, we will describe synthesis and characterization of heterobimetallic systems utilizing a tripodal ligand framework that allows for coordination of lanthanides in the +3 oxidation state along with a secondary metal that can tune the properties of the bound lanthanide. The ligand system can incorporate a variety of secondary metals, enabling a wide range of tunability. In the case of europium complexes, electrochemical studies have been used to study the Eu(III/II) redox manifold across a range greater than 500 mV. Our most recent work will be discussed, including extension of our approach to other lanthanides and structural results from XRD that provide insight into the observed tuning effects.

Tuning access to europium in the +2 oxidation state

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