Assembling diuranium complexes in different states of charge with a bridging redox-active ligand

Abstract

Radical-bridged diuranium complexes are desirable for their potential high exchange coupling and single molecule magnet (SMM) behavior, but remain rare. Here we report for the first time radical-bridged diuranium(IV) and diuranium(III) complexes. Reaction of [U{N(SiMe₃)₂}₃] with 2,2′-bipyrimidine (bpym) resulted in the formation of the bpym-bridged diuranium(IV) complex [{((Me₃Si)₂N)₃U^IV}₂(μ-bpym²⁻)], 1. Reduction with 1 equiv. KC₈ reduces the complex, affording [K(2.2.2-cryptand)][{((Me₃Si)₂N)₃U}₂(μ-bpym)], 2, which is best described as a radical-bridged U^III–bpym˙⁻–U^III complex. Further reduction of 1 with 2 equiv. KC₈, affords [K(2.2.2-cryptand)]₂[{((Me₃Si)₂N)₃U^III}₂(μ-bpym²⁻)], 3. Addition of AgBPh₄ to complex 1 resulted in the oxidation of the ligand, yielding the radical-bridged complex [{((Me₃Si)₂N)₃U^IV}₂(μ-bpym˙⁻)][BPh₄], 4. X-ray crystallography, electrochemistry, susceptibility data, EPR and DFT/CASSCF calculations are in line with their assignments. In complexes 2 and 4 the presence of the radical-bridge leads to slow magnetic relaxation.