Reactivity of a New Zirconium Phosphonate Phase, Zr2(O3P-CH2CH2-bipyridiniumCH2CH2-PO3)X6·2H2O, Toward Organic and Inorganic Monophosphonates

We report that zirconium viologen diphosphonate, (Zr2(O3P-CH2CH2-bipyridinium-CH2CH2PO3)X6·2H2O), where X=halide ion, ZrVP, will react with a variety of phosphonates (H2O3P-R, where R=OH, H, CH3, C6H5) under mild conditions, producing a disordered porous phase. This is in sharp contrast to the observed reactivity of the more common zirconium phosphonate phases: the ALPHA-phase group (IVB) layered phosphonates Zr(O3PR)2 (whose structures are based upon ALPHA-(Zr(O3POH)2·H2O), ALPHA-ZrP) are resistant to reaction with monophosphonates while GAMMA-Zr(O4P)(O2P(OH)2)·2H2O, GAMMA-ZrP, undergoes topotactic ligand exchange with mono- and di-phosphonates to form ordered porous materials. We follow the reaction by Xray powder diffraction and IR and UV spectroscopies and investigate the porous nature of the resulting solids through ion-exchange and N2 adsorption experiments.