Molecular Mechanisms of Spin Crossover in the {Fe(pz)[Pt(CN)4]} Metal–Organic Framework upon Water Adsorption

The rational design of multifunctional materials with properties that can be selectively controlled at the molecular level is key to the development and application of nanoscale devices. In this study, molecular dynamics simulations using ligand-field molecular mechanics are performed to elucidate, for the first time, the molecular mechanisms responsible for the variation of the spin-crossover properties of the {Fe(pz)[Pt(CN)4]} metal–organic framework upon water adsorption. The simulations demonstrate a direct relationship between the water loading adsorbed in the pores and the variation of the spin-crossover transition temperature, with the high-spin state of the material becoming gradually more stabilized as the number of adsorbed water molecules increases. The decrease of the spin-crossover temperature of {Fe(pz)[Pt(CN)4]} upon water adsorption predicted by the simulations is in agreement with the available experimental data and is traced back to the elongation of the bonds between the Fe(II) atoms an...