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Solar fuels research aims to mimic photosynthesis and devise integrated systems that can capture, convert, and store solar energy in the form of high-energy molecular bonds. Molecular hydrogen is generally considered an ideal solar fuel because its combustion is essentially pollution-free. Cobaloximes rank among the most promising earth-abundant catalysts for the reduction of protons to molecular hydrogen. We have used multifrequency EPR spectroscopy at X-band, Q-band, and D-band combined with DFT calculations to reveal electronic structure and establish correlations among the structure, surroundings, and catalytic activity of these complexes. To assess the strength and nature of ligand cobalt interactions, the BF(2)-capped cobaloxime, Co(dmgBF(2))(2), was studied in a variety of different solvents with a range of polarities and stoichiometric amounts of potential ligands to the cobalt ion. This allows the differentiation of labile and strongly coordinating axial ligands for the Co(II) complex. Labile, or weakly coordinating, ligands such as methanol result in larger g-tensor anisotropy than strongly coordinating ligands such as pyridine. In addition, a coordination number effect is seen for the strongly coordinating ligands with both singly ligated LCo(dmgBF(2))(2) and doubly ligated L(2)Co(dmgBF(2))(2) . The presence of two strongly coordinating axial ligands leads to the smallest g-tensor anisotropy. The relevance of the strength of the axial ligand(s) to the catalytic efficiency of Co(dmgBF(2))(2) is discussed. Finally, the influence of molecular oxygen and formation of Co(III) superoxide radicals LCo(dmgBF(2))(2)O(2)(•) is studied. The experimental results are compared with a comprehensive set of DFT calculations on Co(dmgBF(2))(2) model systems with various axial ligands. Comparison with experimental values for the "key" magnetic parameters such as g-tensor and (59)Co hyperfine coupling tensor allows the determination of the conformation of the axially ligated Co(dmgBF(2))(2) complexes. The data presented here are vital for understanding the influence of solvent and ligand coordination on the catalytic efficiency of cobaloximes.

The Hydrogen Catalyst Cobaloxime: A Multifrequency EPR and DFT Study of Cobaloxime’s Electronic Structure