Effects of Substituents on the Molecular Structure and Redox Behavior of Uranyl(V/VI) Complexes with N3O2‑Donating Schiff Base Ligands

Uranyl(VI) complexes with pentadentate N3O2-donating Schiff base ligands having various substituents at the ortho (R1) and/or para (R2) positions on phenolate moieties, R1,R2-Mesaldien2−, were synthesized and thoroughly character-ized by 1H NMR, IR, elemental analysis, and single crystal X-ray diffraction. Molecular structures of UO2(R1,R2-Mesaldien) are more or less affected by electron-donating or -withdrawing nature of the substituents. The redox be-havior of all UO2(R1,R2-Mesaldien) complexes were investigated to understand how substituents introduced onto the ligand affect redox behavior of these uranyl(VI) complexes. As a result, the redox potentials of UO2(R1,R2-Mesaldien) in DMSO increased from −1.590 V to −1.213 V with an increase in the electron-withdrawing nature of the substituents at the R1 and R2 positions. The spectroelectrochemical measurements and theoretical calculation (DFT and TD-DFT calculations) revealed that the center U6+ of each UO2(R1,R2-Mesaldien) complex undergoes one-electron reduction to afford the corresponding uranyl(V) complex, [UO2(R1,R2-Mesaldien)]−, regardless of difference in the substituents. Consequently, the redox active center of uranyl(VI) complexes seems not to be governed by the HOMO/LUMO gap, but to be determined by whether the LUMO is centered on a U 5f orbital or on one π* of a surrounding ligand.