Axially Symmetric U-O-Ln- and U-O-U-Containing Molecules from the Control of Uranyl Reduction with Simple f-Block Halides

The reduction of U-VI uranyl halides or amides with simple Ln(II) or U-III salts forms highly symmetric, linear, oxo-bridged trinuclear U-V/Ln(III)/U-V, Ln(III)/U-IV/Ln(III), and U-IV/U-IV/U-IV complexes or linear Ln(III)/U-V polymers depending on the stoichiometry and solvent. The reactions can be tuned to give the products of one- or two-electron uranyl reduction. The reactivity and magnetism of these compounds are discussed in the context of using a series of strongly oxo-coupled homo-and heterometallic poly(f-block) chains to better understand fundamental electronic structure in the f-block.