Interludes And Winding Metal - Organic Framework Compounds To Build And Performance Study

The research priority of coordination functional material is changing from synthesis, structure characterizations to functional properties, its characteristics are mainly embodied in two aspects:investigate the relationship of structure and property and explore advanced composite material with more superior properties. Employment of related principle molecular designing and crystal engineering was used to modify and assemble the metal-organic frameworks(MOFs) polymers materials and would be boost the novel topological frames and special functions of the sets, which has been greatly attracted in the materials field. In addition, entanglement and interpenetration is a popular phenomenon in the macrocosm, however, in the microcosm system; it is not universal due to the structural particularity of its own. Entangled and interpenetrated examples are always observed in MOFs compounds, which exhibit common types:including 0D→1D;1D→1D;1D→2D;1D→3D;2D→2D; 2D→3D; 0D+0D→1D,1D+2D→3D, and so on. As structure determines property, structural peculiarity of entangled and interpenetrated networks will reinforce the skeleton rigidity and porosity of the whole frame, thereby generating some peculiar functional properties, which became a new research hotspot in coordination chemistry.The aim of this thesis is to prepare new types of entangled MOFs compounds on the basis of flexible ligands and transition metal, to study the synthetic conditions and rules for these compounds, discuss the topological types, and to explore the relationships between structures and properties for the sets of compounds. This work includes five chapters.1. Chapter 1 gives an introduction of the definition, development history, classify and potential functions of MOF compounds, especially, discuss the synthesized methods, the characteristics of types of entanglement and interpenetrated MOFs compounds and their peculiar functional properties, as well as the program of novel entanglement and interpenetrated MOFs compounds. The aim and progress of this work have been outlined.2. In chapter 2, by mixing a typical example of a long, V-shaped, flexible ligand 4,4'-oxybis(benzoic acid) (H2oba) and N-containing ligands in the presence of transition metal ions, nine coordination polymers have been synthesized, which have kinds of dimensions, topological types and functional properties. Three isologues of compounds 1-3 have unprecedented topologies, which present the first example of 4-crossing catenane motifs. The effect of metal ions on the structures and properties of MOFs was also discussed.3. In chapter 3, by mixing flexible hydroxycarboxylic acid and assistant ligands in the presence of transition metal ions, a series of compounds have been prepared, which exhibit zero-dimensional to three-dimensional structural frames. It has been demonstrated that the coordinated modes of ligands of hydroxycarboxylic acid, the size of assistant ligand and the synthesis conditions are critical to the resulting architectures. Besides, the heterometallic compound 14 has a strong antimagnetic behavior, which has been theoretically calculated and simulated for its magnetism, while polymer 13 features a strong ferromagnetism.4. Chapter 4 reports the coordination chemistry of 1H-imidazo[4,5-f][1,10]-phenanthroline in the absence/presence of the different conformations of carboxylate under mild conditions, series of compounds have been obtained. The result indicates that new interpenetrating and entangled MOFs higher-nuclear compound can be obtained successfully by introducing flexible multi-carboxylate ligands, the metal radium affects the dimensions obviously. Some of compounds exhibit strong luminescence characters.5. In chapter 5, two types of interpenetrating and entangled MOFs polymers are synthesized by solvthermal reactions. The first one is composed of sextuple-stranded molecular braid, which represents the highest stranded number of molecular braid; the second set features threefold 2D→3D parallel interpenetrated net with a Schlafli symbol of 22.48.65 and contains one interesting Co2(CO2)4 paddle-wheel unit.