Two- and Three-Dimensional Heterometallic Ln[Ru-α-Ammonium Diphosphonate] Nets: Structures, Porosity, Magnetism, and Proton Conductivity.

By virtue of its magnetic moment and variable valencies, the paddlewheel ruthenium dimer is a desirable molecular building block for the construction of functional networks. If in addition to the Ru open axial site the organic ligand is designed to allow transversal connections, a wider range of structural possibilities is expected. The organic ligand can also be modified to introduce other functionalities. In the present study we employed a diphosphonate containing a protonated amine, 1-ammoniummethylenediphosphonate [NHCH(PO); (Hamdp)], as the ligand to construct paddlewheel Ru(Hamdp) building block. Three networks of different structural dimensionalities were obtained. (HO)[Ru(Hamdp)] () forms one-dimensional chain of = 1 Ru bridged at axial positions through Ru-O bonds. From as a starting material, its reaction with lanthanide ions results in the bimetallic Dy(HO)[Ru(Hamdp)][Ru(Hamdp)(HO)][Ru(Hamdp)(amdp)]·12HO (), which has a pillared-bilayer structure and Yb[Ru(Hamdp)][Ru(Hamdp)(HO)]·15HO (), which is a three-dimensional open framework, both contain mixed-valent Ru units and show new connection topologies of the Ru dimers. After activation does not adsorb N and CO but takes up 12 HO. In contrast, take up all three gases. The optimum proton conductivities were moderate reaching 1.44 × 10 for and 0.93 × 10 S cm for at 95% relative humidity and 55 °C.