A series of three tetranuclear and two trinuclear Co(III) carboxylate complexes are synthesized and thoroughly spectroscopically and electrochemically characterized. The relative stability of the tetranuclear versus trinuclear complexes is investigated by density functional theory calculations, and the infrared and ultraviolet/visible spectra are calculated to deconvolute contributions of the tetranuclear and trinuclear Co-oxo core from those of the organic ligands, respectively.

Heterocubane-type complexes containing a central [Co^III ₄O₄] core have received increasing interest as surface cutouts of active spinel-type Co₃O₄ water splitting catalysts. The synthesis of a series of tetranuclear ([Co₄O₄(O₂CR)₄(py)₄] (R = Me 1, Et 2, n-Pr 3)) and trinuclear Co(III) carboxylate complexes [Co^III ₃(μ₃–O)(μ₂–OH)(O₂CR)₃(py)₅](NO₃)₂ (R = i-Pr 4, t-Bu 5) and their structural (single-crystal X-ray diffraction) and spectroscopic (except 5, ¹H NMR, UV/vis, IR) characterization is reported. Quantum chemical calculations using density functional theory show that the relative stability of the tetranuclear complexes versus the trinuclear complexes decreases with increasing steric demand of the carboxylate ligand. In addition, the UV/vis and IR spectra of the tetranuclear complexes are calculated to deconvolute contributions from the carboxylate ligands and the Co-oxo core. Furthermore, the electrochemical properties of the complexes 1–4 are studied by cyclic voltammetry, demonstrating that the redox potential of the complexes correlates with the steric demand of the carboxylate ligand.