Design,Synthesis And Properties Of Copper Halide Clusters

The metal halogen compounds have received attractive attention in recent years because of their complex structures,topological diversities and good physical and chemical properties.However,most of the metal halogen compounds that have been reported till date are constructed with the metal centers of individual atoms and organic ligands,while metal clusters acting as metal centers of the coordination polymers are rare.Compare with a single metal center,multinuclear complexes have selective coordination modes due to the presence of multiple coordination centers,which is more favorable for the preconditioning of the structure and could enhance the functional properties of these hybrid materials.In addition,due to the presence of cluster units,the complexes can exhibit some unique properties,such as good optical,electrical and magnetic properties.Such complexes with cluster units have their own unique advantages,especially in the assembly of functional materials with special applications in adsorption,separation,luminescence,and catalysis.Hence the construction of metal cluster complexes is of great significance.In this thesis,a series of metal cluster complexes have been constructed with copper halide clusters as structural units.The thesis is divided into four chapters with the first chapter focused on the research background and relevant discussion on the theoretical aspects of copper halide clusters.In the second chapter,we discussed the experimental procedures and corresponding structural descriptions of a series of copper halide clusters based zeolitic cluster organic frameworks which were synthesized using hexamethylenetetramine(hmt)ligand.The tetrahedron-like molecular structure shaped hmt ligand with four N-atoms mimics the structure of SiO4 and has been advantageous for the preparation of different frameworks with vivid topologies.Zeolitic cluster organic frameworks constructed with two different tetrahedral units,hexamethylenetetramine(hmt)and hint-type[Cu4Cl6]2-clusters,are realized in this work for the first time.By using a tetrahedral hmt ligand to assemble in situ hmt-type Cu4Cl6 clusters,a three-dimensional cluster organic framework with lonsdaleite(Ion)topology is successfully built to host the two-dimensional honeycomb-like metal-organic complex.Furthermore,by systematic adjustment of the reaction conditions,a series of cluster organic frameworks based on hmt and other well-defined copper-halide clusters,such as Cu2Cl3,Cu3Cl2,Cu4Cl4,Cu5Cl6,and Cu6Cl6,are also presented,which exhibit rich topological nets.These compounds are further investigated by infrared,powder X-ray diffraction,thermogravimetric analysis and photoluminescent spectroscopy.The detailed characteristic properties of these novel hybrid materials are well discussed.In the third chapter,four cluster compounds with[Cu12S6]clusters were prepared by solvothermal method using hexamethylenetetramine and cuprous halides namely[Cu12(SCH3)6(H2O)12][Cu12(SCH3)6Cl12](6),[Cu12(SCH3)6(H2O)12][Cu12(SCH3)6Br12](7),[Cu14(?-SCH3)6(?3-Cl)4(?2-Cl)4(DMSO)2](8),[Cu20(SCH3)6Cl14(hmt)2](9).Crystals(6)and(7)are zero-dimensional structures,which are supramolecular ion pair composed of spherical anionic-cationic copper sulfide clusters;crystal(8)is an inorganic copper sulfur halide cluster compound having a two-dimensional layered structure;crystal(9)is a three-dimensional compound with twenty nuclear copper sulfur halide clusters.The fluorescence properties of the compounds were studied.It is found that the crystals(6)and(8)exhibit unusual mechanochromic properties.In chapter 4,two copper(I)halide-based coordination polymers namely,[Cu3Cl2(Tipa)2]Cl(10),(Tipa=tris(4-(1 H-imidazol-1-yl)phenyl)amine)and[Cu3I3(CuI)2(Tipa)3](11)were synthesized by solvothermal reactions using a large ligand Tipa(Tipa = 2,4,6-tris(p-imidazolyl)amine).crystal(10)exhibits unusual mechanochromic and photocatalytic methylene blue(MB)dye degradation properties.We found that halogen ions played a very important role in regulating the structure and physical properties of complexes under similar reaction conditions.