Two molybdophosphate compounds,[Ni（bim）3]2[H2P2Mo5O23]·2H2O 1 and [Zn（bpy）2]2[Zn（bpy）（H2O）]2Zn[Mo6O12（OH）3（HPO4）4]2·9H2O 2 （bim = 2,2＇-biimidazole,bpy = 2,2＇-dipyridyl）,have been synthesized under hydrothermal conditions and structurally characterized by elemental analysis,TG,and IR. The single-crystal X-ray analysis exhibits that 1 consists of one [H2P2Mo5O23]4-,two [Ni（bim）3]2＋ cations and two lattice water molecules,while 2 is constructed from one sandwich-type [ZnP4Mo6] anion modified by four Zn-bpy complexes and nine lattice water molecules. The electrochemical behaviors of compounds 1 and 2 have been studied in detail based on solid bulk modified carbon paste electrodes of compound （CPEs）.
A supramolecular compound（H2en）2[Cu（en）2（H3O）2][Mo8O28]（en=ethylenediamine） was hydrothermally prepared and confirmed by elemental analysis and TG analysis.Single-crystal X-ray analysis reveals that the crystal crystallizes in the triclinic system,space group P1 with a=9.4635（4）,b=9.8645（5）,c=10.9794（5）A,α=69.2050（10）,β=72.3730（10）,γ=78.4510（10）o,Mr=1559.55,V=908.24（7）A^3,Z=1,Dc=2.851 g/m^3,F（000）=749,μ=3.350 mm^-1,S=1.000,the final R=0.0217 and wR=0.0567.The compound consists of（H2en）^2＋,[Mo8O28]^8-anion and [Cu（en）2（H3O）2]^2＋ cations and constructs a 3D supramolecular structure through hydrogen bonds between the nitrogen atoms from en of [Cu（en）2（H3O）2]^4＋ fragments and the terminal oxygen atoms from the [Mo8O28]^8-polyoxoanions.The electrochemical behavior of this compound has been studied in detail based on a solid bulk modified carbon paste electrode of compound（CPE）.
Three new one-dimensional compounds [{NaO2（H2O）2}2{（M（H2O）2）2（WO2）2- （BiW9O33）2}]·16H3O＋·XH2O （M = MnII （1）, CoII （2）, NiII （3）） have been synthesized in an aqueous solution, and structurally characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. These tungstobismuthates reveal that one common feature is the trivacant β-B-BiW9O33 Keggin fragment as the structural building unit. Two β-B-BiW9O33 units are connected by two WO2 groups with further stabilization by the addition of two M（H2O）22＋ groups leading to the M2Bi2W20 anions, which are linked in a 1-D chain by bisodium cluster. Electrochemical analyses show that compounds 1-3 display unique redox properties and good electrocatalytic activity to reduce nitrite.
