Calorimetric and neutron diffraction studies on transitions of water confined in nanoporous copper rubeanate

Copper rubeanate (H(2)C(2)N(2)S(2)Cu) has a nanoporous structure and exhibits high proton conductivity with adsorbing water inside the pores. We have studied the phase behavior and structure of the water confined in copper rubeanate hydrates (H(2)C(2)N(2)S(2)Cu.nH(2)O, n = 0, 2.1, 3.7) by adiabatic calorimetry and neutron powder diffraction. In the hydrate samples, a glass transition and a first-order transition appeared around 150 and 260 K, respectively. The transition entropy was similar to the entropy of fusion of bulk water, indicating that the adsorbed water is disordered above the transition temperature, like bulk water, and ordered below 150 K, like bulk ice. The neutron diffraction data demonstrated that both dry and hydrated copper rubeanates have amorphous structures over the temperature range 100-340 K. The analyses on the diffraction peak owing to the adsorbed water revealed that the transition at 260 K is a liquid-liquid transition due to the condensation of water on the surface of the pores, and the condensed water molecules are gradually ordered below 260 K and frozen-in at the glass transition around 150 K.