Hydrothermal Synthesis, Structure And Properties Of Metal Phosphorus (phosphonate) Salts

Microporous materials have attracted increasing attention owing to their rich structural chemistry and potential applications in the domains of catalysis,gas storage,adsorption,ion exchange and separation.The aim of this thesis is to explore the hydrothermal/ solvothermal preparation of metal phosphates/phosphites materials by selecting different types of SDAs as ligands or utilizing the in-situ N-alkylation transformations of templates.The structures of these compounds have been determined by single-crystal X-ray diffraction,and further characterized by elemental analysis,IR,powder X-ray diffraction,thermogravimetric and fluorescence analysis.And our work is mainly focused on:1.By selecting phosphoric acid in methanol-aqueous solutions,chooseing different types of organic amines?1,4-diazabicyclo[2,2,2]octane,1-methylpiperazine?as organic SDAs,we have realized a series of aluminophosphates:[dmdabco][Al₂?HPO₄?₄]?3-1?,[tmpip]0.5[Al?HPO₄?₂]?3-2?,[tmpip][Al₆?PO₄?₆?HPO₄?] ??H₂O??3-3?have been synthesized under hydrothermal conditions.Compound 3-1 and 3-2 are isostructural and exhibit infinite inorganic chain built from AlO₄ and HPO4 tetrahedra;compound 3-3 featrues an rarely observed Al/P ratio of 6/7 and has a three-dimensional open-framework constructed from AlO₄,AlO₅,PO₄ and HPO₄ units.2.Based on the assembly of phosphite in the presence of different organic amines,we syntheize three phosphite zinc compounds under hydrothermal conditions :[dmdabco][Al₂?HPO₄?₄]?3-1?,[tmpip]_0.5[Al?HPO₄?₂]?3-2?,[tmpip][Al₆?PO₄?₆?HPO₄?] ??H₂O??3-3?.The frameworks of 3-4-3-6 are constructed from the 4-connected ZnO4 tetrahedra and 3-connected HPO3 pseudo-pyramids with distinct connection mode driven by different organic amine templates.There are 12-membering ring?12-MR?and 8-MR apertures in the?3,4?-connected 3D architecture of 3-4-3-6.It is notable that helical chains are observed in the framework of compound 3-6.3.Based on selecting organophosphine?hydroxyethylididene diphinic or nitrilotri methylenephosphonic acid?three new transition-metal triphosphonates decorated with neutral rigid N-containing ligands have been solvothermally prepared and structurally characterized.The compounds 4-1 and 4-2 possess pillar-layer structure,in which the transition-metal-triphosphonates act as layers and the rigid tib ligand serve as pillars.Compound 4-1 exhibits intense blue luminescence;while compound 4-2 exhibit weak ferromagnetic behaviour.The layered framework of compounds 4-3 was composed of 1-hydroxyethylidenediphosphonate and zinc ion.The most interest features rapid photochromism upon irradiation with sunlight or UV light at ambient temperature.