Cation coordination polyhedra lead to multiple lengthscale organization in aqueous electrolytes.

Understanding multiple lengthscale correlations in the pair distribution functions (PDFs) of aq. electrolytes is a persistent challenge. Here, the coordination chemistry of polyoxoanions supports an ion-network of cation-coordination polyhedra in NaNO 3(aq) and NaNO 2(aq) that induce long-range solution structure. Oxygen correlations associated with Na + -coordination polyhedra have two characteristics lengthscales; 3.5-5.5 Å and 5.5-7.5 Å, the latter solely associated oligomers. The PDF contraction between 5.5-7.5 Å observed in many electrolytes is attributed to the distinct O⋯O correlation found in dimers and dimer subunits within oligomers.