Crystal Engineering In Ionic Liquids--Designing Synthesis And Characterization Of Organic-inorganic Hybrid Materials

Aiming at synthesizing new materials, the scientists have been investigating new synthetic reactions, discovering new synthetic methods and developing new synthetic techniques. Organic-inorganic hybrid materials have been extensively studied due to their potential applications of such materials to living tissues, photochemistry, electromagnetism, catalysis, adsorption, and so on. Since the organic-inorganic hybrid compounds consist of inorganic and organic compositions, the compounds usually show combined properties of inorganic and organic compositions. Recently, a method based on self-organization under solvothermal conditions has been developed to prepare organic-inorganic hybrid materials. Under solvothermal conditions, certain properties of the solvent, such as density, viscosity and diffusion coefficient change dramatically and the solvent behaves much differently from what is expected at general conditions. Consequently, the solubility, the diffusion behavier and the chemical reactivity of the reactants (usually solids) are greatly increased or enhanced. This enables the reaction to take place at a much low ?temperature. By this convenient method, many novel organic-inorganic hybrid compounds have been synthesized.The borophosphate compounds are similar to aluminosilicates and aluminophosphates in the topology structures and properties. Owing to the synergistic interactions of borate groups and phosphate groups, the novel physical and chemical properties of the borophosphate compounds will have potential applications in catalysis, ion exchange and molecular sieve etc, and the systematic investigations of new borophosphates are currently of great interest due to potential nonlinear optical properties and application as magnetism, ferric-electric and pressure-electric functional materials. The crystal engineering of two- and three-dimensional metal coordination polymers is currently another research hotspot due to the potential properties of the materials, such as electrical conductivity, magnetism, host-guest relationships and catalysis. The notable characteristic for characteristic for synthesizing this kind of the materials is that the designed and prepared coordination polymer can be obtained by using structural units acted as molecular building blocksof crystal formation. The synthetic process of the compounds can basically realize the crystal engineering from molecules to crystals and from micro-properties to macro-properties.This work is mainly focused on designing new reactions, synthesizing new compounds, finding new synthetic methods and enhancing the development of solvothermal technique, gradually establishing relationships between solvent and structure, and subsequently designing molecules and controlling material properties. In this thesis, by using organic components as templates or ligands, adjusting reaction conditions and studying an influence of solvent on structures we obtained two organic-inorganic hybrid phosphate and borophosphate, and one layered supramolecular compound with novel topology structures under solvothermal conditions using ionic liquids as solvents. Single crystal X-ray diffractions reveal that the structures of these compounds have notable characteristics, such as one-dimensional straight chain structures, three-dimensional organic-inorganic sandwich-type supramolecular architecture as well as coordination polymer. Also, the supramolecular architecture that cation layer are alternately stacked with anionic layer has rich structural characteristics. Thermal analysis, optical spectroscopy and etc will be discussed in this thesis.By employing ionic liquids as a medium and aiming at speeding up the technical development of solvothermal synthesis, our results had demonstrated that the ionic liquids are very valuable solvent for the crystal engineering of borophosphates, metal coordination polymers and other new materials. With ionic liquids as solvents, such compounds that can not been prepared in traditional solvents have been obtained: (1) one-dimensional straight-...