Study On The Synthesis And Properties Of Coordination Polymers Based On Copper Iodine Clusters And Polymetallic Oxygen Clusters

Coordination polymers(CPs)are made by linking inorganic and organic units by strong bonds to form a new kind of functional materials.This materials with different constituents' geometry,size and kinds of functionality can be varied has led to many different CPs being synthetized and studied within the past decade.Among them,single-crystal-to-single-crystal(SCSC)transformation and CPs which based polyoxometalates(POMs)have been paid widespread attention.In this paper,solvothermal/hydrothemal synthesis method were used and the main contents of this paper are listed as follows:1.We described the transformation of two semblable compounds{H3[Cu4I3(TTTMB)2][CuI3][Cu3I4(TTTMB)]2·8H2O}(1)and{H3[Cu6I7(TTTMB)2][Cu3I4(TTTMB)]2[Cu5I6(TTTMB)2]}(2).These two compounds which synthesized by 1,3,5-tris(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene(TTTMB)and copper(?)salt are based on different iodine copper(?)clusters.Interestingly,both compound 1 and 2 can transform to compound{H2[Cu14I16(TTTMB)2]}(3)induced by copper(?)halide salt.Compound 1 and 2 are 2D layer,and compound 3 is 3D network structure.So it includes a change from 2D layers to 3D CPs.The transformation firstly happens in the surface of mother crystal compound 1 or 2 and then slowly generates compound 3.Meanwhile,we study the stabilities of three compounds in air and different pH solutions.In addition,compound 1 and compound 3 show electrical conductivity,and they are promising for potential semiconductor materials in the future.2.We have synthesized two compounds:{[Ni2(TTTMB)2(H20)6][SiW12O40]}(4)and[Mn(H2O)6]{H[PMo9O31](TTTMB)}(5),which are based on[SiW12O40]4-,TTTMB and two transition metals under hydrothermal conditions.In this chapter,we discussed the structure of compound 4 and 5.Compound 4 is built by TTTMB and Ni ions to generate a 2D double layer parallel,and compound 5 has novel structure wuich is built by[PMo9O31]3-and TTTMB through coordinate bond between Mo and N atoms directly.The stabilities of compound 4 in air is also studied.We made a series of experiments to explore the reactions of other metal ions,TTTMB and keggin POM.This can be provided the theoretical bases for designing more compounds in future.3.We got two compounds:{H10[Cd(P2Mo5O23)2(H2O)4](C32H18N12)·3H2O(6)and {H3[PMo12O40](C32H18N12)·3H2O}(7)which synthesized by Tetra(4-imidazolyl)porphyrin(TImP),Na2MoO4 and transition metals.In compound 6,Cd and[P2Mo5O23]6-are connected through coordination bond,but TImp crystallized together without coordination bond.In compound 7,[PMo12O40]3-and TImp crystallized together without coordination bond.We also made a series of experiments to explore the reactions of TImP and other metal ions and POM.It offers the guide for designing more compounds in future.