Survey on the Phase Transitions and Their Effect on the Ion-Exchange and on the Proton-Conduction Properties of a Flexible and Robust Zr Phosphonate Coordination Polymer

The flexible zirconium tetraphosphonate coordination polymer with formula Zr(O3PCH2)(2)N-C6H10-N-(O3CH2P)(2)X2-xH2+x center dot nH(2)O (X = H, Li, Na, K, 0 < x < 1, 4 < n < 7.5) (1) possesses an open framework structure with ID cavities decorated with polar and acids P=O and P-OH groups. 1 has been fully protonated by adding HCl and then subjected to several acid base ion-exchange reactions with alkaline metals hydroxides. 1 is a very robust coordination polymer because it can be regenerated in H- form using strong acid solutions and ri-exchanged several times without hydrolysis and loss of crystallinity. The flexibility of 1 has been also studied by means of TDXD (temperature dependent X-ray diffraction) evidencing remarkable phase transformations that lead to a different disposition of the water molecules. These transformations also influence the accessibility of the cations on the P-OH groups placed inside the channels and thus the ion-exchange properties. The dependence of the proton conductivity properties on these phase transitions has been also investigated and discussed.