Hexaniobate Cluster Anion Monolayers on Gold Nanoparticles: A New Structural Role for Alkali Metal Countercations

Monolayer shells of polyoxotungstate cluster anions on gold nanoparticles in water were electrostatically stabilized by structurally integrated countercations, with formation constants, K, increasing in the order: Li⁺ < Na⁺ < K⁺ < TMA⁺ < Cs⁺ (TMA⁺ = tetramethylammonium). We now report that for hexaniobate cluster anions, K values increase in the same order, with the notable exception of TMA⁺, which is effectively unable to induce monolayer formation. These findings point to a new structural model in which hexaniobate anions form a spherical coordination polymer at the gold surface with alkali metal countercations serving as single-atom structural building units between hexaniobate linkers.