Two- and Three-Dimensional Heterometallic Ln[Ru2-α-Ammonium Diphosphonate] Nets: Structures, Porosity, Magnetism, and Proton Conductivity

By virtue of its magnetic moment and variable valencies, the D4h 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 [NH3CH(PO3)23–; (Hamdp)], as the ligand to construct paddlewheel Ru2(Hamdp)2 building block. Three networks of different structural dimensionalities were obtained. (H3O)2[RuII2(Hamdp)2] (1) forms one-dimensional chain of S = 1 RuII2 bridged at axial positions through Ru–O bonds. From 1 as a starting material, its reaction with lanthanide ions results in the bimetallic Dy(H2O)3[Ru2(Hamdp)2][Ru2(Hamdp)2(H2O)2][Ru2(Hamdp)(amdp)]0.5·12H2O (2), which has a pillared-bilayer structure and Yb[Ru...