Redox Active Hexanuclear Mixed Valence Dicationic Ce(III)/Ce(IV) Coordination Clusters

Abstract

A series of mixed valence hexanuclear dicationic coordination clusters containing two µ4‐O2– bridges with general formula M2+(X–)2 [M = CeIV2CeIII4(µ4‐O)2(L–R)4(val)6(H2O)2; 12+, 32+: R = H, 22+: Me; 12+, 22+: X = CeIII2(val)3(NO3)4, 32+: X = NO3] were synthesized, isolated and characterized. The reaction of cerium(III)nitrate hexahydrate with Schiff base ligand (H2L–R) and o‐vanillin (val‐H) under basic condition led to the formation of M2+(X–)2 and the reaction progress was monitored by mass spectrometric studies. The molecular structures of all complexes were unambiguously characterized by single‐crystal X‐ray diffraction. The magnetic susceptibility measurements of M2+(X–)2 showed that the Ce(III) ions are weakly antiferromagnetically coupled. Thermal stability and molar conductivity of M2+(X–)2 were also studied. Complex 32+(X–)2 was further studied by X‐ray photoelectron spectroscopy to confirm the oxidation states of Ce(III/IV) ions. The M2+ cation was shown to catalyze the TEMPO‐free oxidation of functionalized benzyl alcohols quantitatively to the corresponding benzaldehyde derivatives at 100 °C in presence of aerial O2 using DMF as the solvent.