Self-Assembled Nickel-4 Supramolecular Squares and Assays for HER Electrocatalysts Derived Therefrom

Solid-state structures find a self-assembled tetrameric nickel cage with carboxylate linkages, [Ni(N₂S'O)I(CH₃CN)]₄ ([Ni-I]₄⁰), resulting from sulfur acetylation by sodium iodoacetate of an [NiN₂S]₂²⁺ dimer in acetonitrile. Various synthetic routes to the tetramer, best described from XRD as a molecular square, were discovered to generate the hexacoordinate nickel units ligated by N₂S_thioether, iodide, and two carboxylate oxygens, one of which is the bridge from the adjacent nickel unit in [Ni-I]₄⁰. Removal of the four iodides by silver ion precipitation yields an analogous species but with an additional vacant coordination site, [Ni-Solv]⁺, a cation but with coordinated solvent molecules. This also recrystallizes as the tetramer [Ni-Solv]₄⁴⁺. In solution, dissociation into the (presumed) monomer occurs, with coordinating solvents occupying the vacant site [Ni(N₂S'O)I(solv)]⁰, ([Ni-I]⁰). Hydrodynamic radii determined from ¹H DOSY NMR data suggest that monomeric units are present as well in CD₂Cl₂. Evans method magnetism values are consistent with triplet spin states in polar solvents; however, in CD₂Cl₂ solutions no paramagnetism is evident. The abilities of [Ni-I]₄⁰ and [Ni-Solv]₄⁴ to serve as sources of electrocatalysts, or precatalysts, for the hydrogen evolution reaction (HER) were explored. Cyclic voltammetry responses and bulk coulometry with gas chromatographic analysis demonstrated that a stronger acid, trifluoroacetic acid, as a proton source resulted in H₂ production from both electroprecatalysts; however, electrocatalysis developed primarily from uncharacterized deposits on the electrode. With acetic acid as a proton source, the major contribution to the HER is from homogeneous electrocatalysis. Overpotentials of 490 mV were obtained for both the solution-phase [Ni-I]⁰ and [Ni-Solv]. While the electrocatalyst derived from [Ni-Solv] has a substantially higher TOF (102 s^-1) than [Ni-I]⁰ (19 s^-1), it has a shorter catalytically active lifespan (4 h) in comparison to [Ni-I]⁰ (>18 h).