Cationic Metal-halide And Tetrazole Based Organic-inorganic Hybrid Materials

The design and construction of metal-organic crystallinematerials has been a hot topic for many years, due to not only theirfascinating structures and topologies but also their specific ormultifunctional properties. It is an efficient way to construct newMOFs by choosing proper metal ions or metal clusters and organiclinkers. Copper halides exhibit rich connectivity and richphotophysical properties, which make it more easily to constructMOFs with novel structures when connected by organic ligands.The rich coordination modes of the tetrazol ligands afford greatsynthetic possibilities for the design and preparation ofmetal-organic framework. Here we report the copper halide and1H-tetrazole based metal-organic frameworks and two 3Dcoordination polymers constructed by Cd, 1H-tetrazole and smallauxiliary ligands containing oxide atoms. The dissertation iscomposed of four chapters. Chapter one is introduction. There are three parts. The first oneis a brief introduction to the structure and design of copper halidecomplexes. The second one introduces the synthesis and recentprocess of tetrazole-based coordination polymers. In the last part,the significance and new results of the dissertation are outlined.In chapter two, four new copper halide compounds [Cu2(tta)Br](1), [Cu4(tta)2Br2] (2), [Cu2(tta)I] (3), and[Cu3(HC-tta)2(IC-tta)(H0.75I0.25-tta)2Cl] (4), were obtained by directreaction of tetrazole with CuX2/CuX under hydrothermal reactionconditions. 1 is a 3D layer-pillar metal organic framework,constructed by 2D (Cu2X)+nlayer andμ4-tta ligands. 2 and 3 are 2Dframework constructed by butterfly anionic cluster (Cu4Br2)2+andμ4-tta ligands. The copper(II) compound 4 contains two kind oflayers A and B, which connected in a ABAB manner to form the 3Dframework. Magnetic measurement conform that compound 4shows canted antiferromagnet behavior.In chapter three, two 3D compounds [Cd2(tta)2(ox)] (5) and[CdCl(tta)(MeOH)] (6) were obtained through the reaction of CdCl2,1H-tta and oxalic acid by changing the reaction solvent. 5 is a 3Dlayer-pillar metal-organic framework constructed by the 2Dcadmium oxalate layer andμ3-tta ligands. 6 is also a 3D frameworkconstructed by the one dimensional [Cd-Cl-Cd] chain andμ3-tta ligands, while the methanol connect to the Cd center as terminalligands. All two Cd compounds display strong blue fluorescenceemissions in the solid state at room temperature, which suggestedthat they may be good blue-light-emitted materials.In the last chapter, a concise conclusion was drawn and aperspective of this work was expected.