Synthesis, Structure And Properties Of The Coordination Polymers With Polynuclear Metal Clusters

The rational design and synthesis of coordination polymers has attracted much attention, not only because of their intriguing variety of architectures and topologies but also owing to their potential applications in gas adsorption and separation, asymmetric catalysis, nonlinear optics and magnetic materials. Among them, the stable porous coordination polymers is the most promising research field, and many porous coordination networks with extremely large surface areas have been constructed, based on the secondary building units (SBUs) concept that have been extensively used in syntheses. In this paper, coordinated polymers with polynuclear metal cluster SBUs have been synthesized through hydro(solvo)thermal technique by using linear carboxylate ligands, V-shaped carboxylate ligands and inorganic seleninic acid. The coordination polymers were characterized by elemental analysis, infrared spectra, XRD, thermogravimetric analysis,X-ray single-crystal diffraction, etc. And some coordination polymers fluorescence properties and magnetic properties are also discussed. This paper includes the following five chapters:In the first chapter, we systematically introduce the basic conception and development of the coordination polymers and the research progress of coordination polymers with polynuclear metal cluster SBUs as well as the significance and the progress made in this topic.In the second chapter, one 3D coordination polymer [CH₃NH₂CH₂]₂[Zn₃(bpdc)₄]·DMF·C₂H5OH·8H₂O (1), has been successfully synthesized by using Zn(â…¡) ion and 4,4'-biphenyldicarboxylic acid. Compound 1 is a two-fold interpenetrating 3D porous framework that contains [Zn₃(OCO)₆] secondary building units, which is a 8-connected -(3,6)-network hex topological structure .In the third chapter , we introduce two novel coordination polymers [CH₃NH₂CH₃]₂[Mn₆(OH)₂(sfdb)₃(COO)₆]·H₂O (2) and [Mn₃(sfdb)₃(H₂O)(DMA)₂]·3H₂O (3) have been generated by flexible and tough V-shaped carboxylate ligands and Mn(â…¡) ion under the solvothermal conditions through select different solvents. The structure of 2 contains trinuclear Mn(â…¡) clusters [Mn₃(μ3-OH)(COO)₆] , is a three-dimensional (3D) cage shape coordination polymer, which can be simplified as a 4-connected diamond network structure. The structure of 3 contains trinuclear Mn(â…¡) clusters [Mn₃(COO)6(DMA)2H2O], which is a 3D infinite network.In the fourth chapter, two new 3D coordination polymers [Co₄(SeO₃)₄] (4) and [Co₃(SeO₃)₃(H₂O)] (5), have been successfully synthesized. 4 and 5 were prepared hydrothermally starting from Co(NO₃)₂ and H₂SeO₃ with or without Na2WO4·2H2O in the same temperature. The 3D structures of 4 and 5 have 1D channels by the 10-membered (Co10) formed. The hydrogen bonding interactions exist in the structure of the coordination polymer 5 result in the 1D channels form different from the coordination polymer 4. The coordination polymers 4 and 5 are a pair of supramolecular isomers.In the conclusion, the structure and function of the five coordination polymers and the influence of solvent and template agent on the coordination polymer structure have been summarized. The research provided a new route for design and synthesis of new functional polymers with polynuclear metal cluster SUBs.