Synthesis, Structures And Properties Of Cluster-based Coordination Polymers Incorporating Cuprous Halides And Sulfur-containing Mixed Ligands

Cluster-based coordination polymers is one of the important area in coordination chemistry and the rapid development of polymeric or cluster-based metal-organic frameworks (MOFs) has led to active discussion of their versatile intriguing architectures and topologies as well as potential applications in, for example, magnetism, catalysis, gas storage, ion exchange, molecular recognition and optical properties, etc. We have devoted more attention to using multicomponent assemblies to design and synthesize polynuclear metal clusters with halide-and sulfur-containing mixed ligands because the incorporation of halides and S-donor as bridges between adjacent transition metal sites is more likely to induce core aggregation. Fortunately, we obtained some novel functional coordination polymers, in which various polynuclear cluster units were successfully introduced to act as secondary building units (SBUs). This thesis is divided into five chapters:In Chapter1, the study background of this work, including the development of coordination and supramolecular chemistry, the guidance of crystal engineering and topology in the construction of cluster-based coordination polymers are concisely introduced, as well as the significance and progress of this work.In Chapter2, two copper and one cobalt complexes were synthesized with a6-Anilino-1,3,5-triazine-2,4-dithiol ligand through solvothermal reactions. They show diverse structures and dimensionalities resulted from the unexpected ligand reaction or different coordination geometries of metal ions, which can be tuned by the reaction conditions. The results obtained here provide a hint for synthesizing new cluster-based structures of functional materials by using multifunctional sulfur-containing ligand with interesting side group. We have successfully explained the formation of the new ligands and complexes in the reaction conditions.In Chapter3, we have constructed a luminescent acs topological framework featuring an unprecedented six-connected, trigonal-prismatic [Cu11Br2S6] SBU. The solid-state luminescence spectrum displays a strong red emission band at room temperature. The results obtained here provide a hint for synthesizing new cluster-based MOF structures of functional materials using multicomponent assembly strategy. Halide and sulfur atom facilitate the formation of polynuclear metal clusters as multi-connected SBUs in the construction of fantastic topological frameworks.In Chapter4, we successfully synthesized and characterized two photoluminescent low-dimensional coordination polymers based on [Cu2I2]n double-stranded stair and novel [Cu6I6]n hexagonal cage chain, respectively. These results give us encouragement that the reaction stoichiometry and the reaction condition play a crucial role in the construction and structural tuning of low-dimensional copper halides coordination polymers. The introduction of a simple monodentate ligand with big π-conjugation system can also result in structural and functional diversity.In Chapter5, we have prepared and characterized two novel coordination polymers in the CuX (X=I, Br)/N-donor ligands system under similar solvothermal conditions. Compound7contains [Cu3I3]n chains that can be regarded as adjacent [Cu3I] units connected together via Cu-I bonds, while8has a3D metal-organic structure based on nine-connected [Cu6Br3] building blocks, interconnected by dpt-linkers. These results indicate that the anions of metal salts and a multidentate ligand with more coordinate sites have significant effect on controlling the synthesis of wonderful polynuclear coordination polymers.Finally, brief conclusions on these work and an outlook are provided.