High-Dimensional Extended-Frameworks Based on Reduced Molybdenum Phosphates[P_4Mo~V_60_(28)(OH)_3]~(9-)

Cd(OAc)_2·2H_2O and MnCl_2·4H_2O were separately introduced to the mixture of MoO_3,H_3PO_4 and bpy. Two new reduced molybdenum phosphate[P_4Mo_6O_(28)(OH)_3]~(9-)({P_4Mo_6}) extended inorganic-organic hybrid supramol-ecular networks(H_2bpy)_2[Cd(H_2O)]_3[Cd(HPO_4)_6(PO_4)_2(OH)_6(MoO_2)_(12)]·5H_2O(1) and(H_2bpy)_3[Mn(H_2O)_2]_2[Mn(HPO_4)_6 (PO_4)_2(OH)_6(MoO_2)_(12)]·10H_2O(2) have been synthesized under hydrothermal techniques.Here,compounds 1 and 2 have been characterized by elementary analyses,IR,TG,and single crystal X-ray diffraction.Compound 1 crystallized in the triclinic,space group P1,a=1.1877(2) nm,b=1.348 5(3) nm,c=1.4108(3) nm,α=106.87(3)°,β=108.09(3)°,γ= 107.92(3)°,V = 1.848 3(6) nm~3,Z = 1;Compound 2 crystallized in the triclinic,space group P1,a = 1.1968(2) nm,b = 1.335 4(3) nm,c = 1.462 0(3) nm,α= 77.58(3)°,β= 67.97(3)°,γ= 76.12(3)°,V = 2.0822(7) nm~3,Z = 1.The polyanion of compound 1[Cd(H_2O)]_3[Cd(HPO_4)_6(PO_4)_2(OH)_6(MoO_2)_(12)]~(2-) is composed of Cd[P_4Mo_6]_2 dimer and tri-nuclear {Cd_3} linkers,which are connected together to form inorganic chains.The polyanion [Mn(H_2O)_2]_2[Mn(HPO_4)_6(PO_4)_2(OH)_6(MoO_2)_(12)]~(3-) of compound 2 exhibits a 2D inorganic layer,consisting of Mn[P_4Mo_6]_2 units linked by the Mn~(2+) ions.These two kinds of inorganic extended structures are further linked with Hydrogen bonds of protonated bpy to construct different 3D supramolecular networks.Simultaneously,the electrochemical property of compound 2 has been explored.