Utility of redox-active ligands for reversible multi-electron transfer in uranyl(VI) complexes

In most cases, redox activity of a UO22+ complex is regarded as metal-centered phenomena, because uranium has small energy gaps amongst 5f/6d/7s subshells thereby exhibiting a wide range of oxidation states commonly from +III to +VI or in some instances even +I or +II. While a wide variety of redox-active ligands are known for transition metal complexes including multi-electron reduction that could facilitate inert bond or small molecule activation, only few such examples are known for UO22+. In this study, three UO22+ complexes bearing alpha-diimine-, o-quinonediimine- and 2,6-diiminopyridinebased
ligands were synthesized which exhibited two redox couples in the range from −0.79 V to −2.02 V vs. Fc+/0 to stepwise afford singly- and doubly-reduced complexes. Unique electronic transitions of UO22+ complexes with a manifold of low-lying excited states helped us to complementarily combine spectroelectrochemistry and time-dependent density functional theory (TD-DFT) calculations to assign the redox-active site in these UO22+ complexes, i.e., whether or not a ligand of interest becomes redox-active. During the whole redox processes observed here, the ligands employed are found to be exclusively redox-active, i.e., non-innocent, while the centered UO22+ is just spectating and remains unchanged, i.e., innocent. Whereas double reduction of UO22+ complexes usually involves breakening of strong U≡O bonds, this is not required in the present examples and therefore may find the basis for the synthesis of new types of uranium molecular catalysts and magnetic materials.