Binding Pocket Response of EDTA Complexes with Alkaline Earth Dications to Stepwise Hydration─Structural Insight from...

We investigate the microhydration structures of complexes of alkaline earth dications and ethylenediaminetetraacetic acid (EDTA) for up to two water molecules, using cryogenic ion vibrational spectroscopy in concert with density functional theory (DFT). The interaction with water shows a clear dependence on the chemical identity of the bound ion. For Mg²⁺, microhydration mostly involves the carboxylate groups of EDTA and does not entail direct contact with the dication. In contrast, the larger ions (Ca²⁺, Sr²⁺, and Ba²⁺) interact electrostatically with the microhydration environment, and this interaction increases in importance with the size of the ion. This trend reflects the ion position in the EDTA binding pocket, which comes closer to the rim of the pocket with increasing ion size.