Structure And Properties Of Complexes Of Heteropolyacids And 2,2-bipyridine-4,4-dicarboxylate / 4-formic Acid Coopper Complexes

Keggin heteropoly acid plays an important role in the development of functional materials.It can be combined with metal organic complexes to form a new organic-inorganic composite.Eleven new organic-inorganic composites were synthesized and characterized by X-ray powder diffraction,X-ray single crystal diffraction,Fourier transform infrared spectroscopy and elemental analysis.details as follows:(l)Mixing Keggin-type heteropoly acid,CuCl2·2H2O and organic ligand 2,2'-bipyridine-4,4'-dicarboxylic acid(H2bpdc)by hydrothermal method at high temperature,And the new type of organic-inorganic composite with six proton-conducting Keggin-type clusters was synthesized for the first time.They are {Cu9(bpdc)6(H2O)4(OH)2[SiW12O40]}·9H2O(1)?{Cu9(bpdc)6(H2O)3(OH)3[PW12O40]}·9H2O(2)?{Cu9g(bpdc)6(H2O)3(OH)3[PMo12O40]}·9H2O(3)?[Cu5(Hbpdc)2(bpdc)2(H2O)4(SiW12O40)]·6H2O(4)?{[Cu(H2bpdc)(Cl)2]2(H2O)[SiW12O40]}·38H20(5)and{[Cu(H2bpdc)(H2O)Cl][Cu(H2bpdc)(H2O)3][PMo12O40]}·25H2O(6).The results of single crystal diffraction analysis show that 1-3 belong to the R3c space group in the trigonal system.The three-dimensional structure of the three kinds of complexes is composed of a polyacid anion surrounded by six metal organic complexes;the space group of the Complex 4 belongs to C2/c in the monoclinic system,there are three kinds of Cu(?)ions in the complex.the dinuclear coordinated Cu2 forms a two-dimensional layer framework on the ab surface and the bc surface by Cul connection,and the poly acid anion is embedded in the framework of the metal organic ligand by a coordination bond to form a two-dimensional layer space structure.In addition,Cu3 in the complex connects the heteropoly acid anion of the adjacent layer through O10,and connects the adjacent two-dimensional organic layer through 024,and forms a three-dimensional structure by the action of the coordination bond.Complex 5 belongs to the orthorhombic system and has a space group of I mmm.It is a novel double-supported Keggin-type organic-inorganic complex based on Cu(?)ions and H2bpdc molecular modification.The complex 6 belongs to the P2/n space group in the monoclinic system.It is a kind of two metal Cu ions containing a six-coordinate octahedral geometry based on Cu(?)ions and H2bpdc molecules.These new Keggin-type organic-inorganic complexs in a certain temperature and humidity range have good proton conductivity.(2)We obtained three new organic-inorganic complexs using Keggin-type heteropoly acid?-H4SiW12O40·24H2O and Hbpdc and CuCl2·2H20,they are{[Cu(Hbpdc)(H2O)2][Cu(Hbpdc)(H2O)2][SiW12O40]}·11.5H2O(7)?{[Cu8(Hbpdc)2(bpdc)6(H2O)2(Cl)2][SiW12O40]2}·5H2O(8)and{[Cu12(bpdc)12(H2O)3(Cl)2][SiW12O40]}H2[SiW12O40](9),The X-ray single crystal diffraction data shows that the composites 7-9 belong to the monoclinic system,but the complexes 7 and 8 belong to the P21/c space group,and the space group of the complex 9 belongs to the R 3 group.Complex 7 is a novel three-supported Keggin-type organic-inorganic composite based on Cu(?)ion and Hbpdc molecular modification,and the molecular unit of the complex is matched.The action of the bit bond forms a one-dimensional chain and the two one-dimensional chains form a one-dimensional double-strand through a short-distance contact between the terminal oxygens of the polyacid anion,and the solvent molecules are filled in the hydrophilic barrel of the three-dimensional structure thereof.Composite 8 is a modified four-supported Keggin-type novel organic-inorganic composite based on Cu(?)ions and Hbpdc molecules.The molecular units in the composite 8 also form two different two-dimensional layers(A and B)due to the different helical directions,and the two two-dimensional layers in the composite are stacked by the ABAB method to form a three-dimensional supramolecular network of the substance.The complex 9 contains different copper ion molecular structural units and Keggin-type heteropoly acid anions to form a novel organic-inorganic composite.The X-ray powder diffraction pattern indicates that the structure of the composite 7-9 was not destroyed before and after the electrochemical AC impedance test,that is,the sample remained after the high humidity,high temperature electrochemical AC impedance test environment,their original structure not be destroyed.Similarly,the impedance test results of the composites 7-9 in the temperature range of 25 degrees Celsius to 100 degrees Celsius and the relative humidity of 35%to 98%can be seen that all three materials have good proton conductivity.(3)We also obtained two cases of novel organic-inorganic complex,which mixed the metal-organic complexes of Keggin-type heteropoly acid ?-H3PW12O40·6H2O and 2,2'-bipyridyl-4,4'-dimethanol(dbhybp)and CuCl2·6H2O at room temperature:{[Cu(dbhybp)(H2O)(Cl)(CH3CN)]2[PW12O40]}·4H2O(10)?{[Cu(dbhybp)2]2(Cl)][PW12O40]}·4H2O(11).The complex 11 differs from the composite 10 is that the Keggin-type heteropolyacid anion in the complex 11 does not participate in coordination but is freed in a two-dimensional layer of its metal organic cluster.