Design,Construction And Properties Of Bifuctiontional Ligand Based Metal-Organic Materials

Metal–organic frameworks?MOFs?are some of the most exciting materials in current science,with an explosive growth since the 1990s.Their utility and diversity of applications depends on a combination of their chemistry,their framework topology and designable fuctional groups of inorganic and organic joints.Herein,employing two bifunctional ligands as the organic structs and a variety of transition/alkali metals as the inorganic center,fourteen complexes with vrious topologies have been successfully constructed upon appropriate synthesis methods and careful regulation of react ion conditions,which excbit excellent performance on magnetism,supercapacitor,thermal expansion and fluorescence.There are five parts dscribed in detial as following:1.A brief introduction has been firstly given based on the development,application,design strategy and synthesis conditions of MOFs.Next,the bifunctional ligands of N-heterocycle ligand are introduced as feasible sythesis strategy to prepare designated MOFs.Meanwhile,C–H bond activation was emphasized to generate bifunctional ligands.Then,supercapacitor and thermal expansion behavior of the complexes are described with detail.At last,the significance and main achievements of the thesis are summarized.2.Hydrothermal treatment of cupric chloride and tetrazole in the presence of hydroiodic acid generated a spin canted coordination polymer Cu₃?tta?₂?Itta?(I_0.25-tta)₂Cl?CP-1?,?Htta=1-H-tetrazole,Itta=5-Iodo-1-H-tetrazole?,showing 3D network constructed by layered[Cu₂Cl?tta?₂]_n^n-and chain-like[Cu?Itta?(I_0.25tta)₂]_n^2n-motifs linked through expensive bifunctional Itta groups in situ C-H iodizated from cheap Htta.3.Hydrothermal treatment of cupric salts and bifunctional 4-?4H-1,2,4-triazol-4-yl?benzoic acid?tzbc?can form four 3D multinuclear cupric cluster based MOFs:[Cu₂?OH??tzbc?₂]NO₃?CP-2?,[Cu₂?tzbc?₂?hdc?]?CP-3??hdc=hexanedioic acid?,[Cu₂?OH?Cl?tzbc?₂]?CP-4?and[Cu₂?OH?Br?tzbc?₂]?CP-5?.Porous CP-2 possesses 3D cationic framework constructed from tzbc and butterfly-like Cu₄ cluster based 1D Cu-O-Cu chain,as the NO₃^-within 1D channel.The paddle-wheel Cu₂ units can be linked by rigid tzbc ligand and flexible htc linker to generate 3D network of CP-3,which exhibits conformational flexibility owing to the flexible assist hdc linker.Butterfly-like Cu₄ cluster with Cu-O-Cu and Cu-Cl/Br-Cu connecty linked by tzbc group can generate 3D hexagonal network of CP-4and CP-5.CP-4 has high electrochemical activity,and the composite material formed with a certain amount of polyaniline can have more than twice the capacitance of the original material.Also,Zn?II?/Cd?II?-based MOFs,[Cd₂?OH??tzbc?₃]?CP-6?,[Cd₂?tzbc??OH?₂?H₂O?₂]?CP-7?,[Zn?tzbc??H₂O?₄]?CP-8?,and[Zn?tzbc?₂]?CP-9?,have also been constructed from tzbc and Zn?II?/Cd?II?salts,which exhibit fluorescence behavior.4.Hydrothermal treatment of bifunctional flexible ligand?FL?5,5'-?propane-1,3-diylbis?oxy??diisophthalic acid?pdta?and LiOH can construct five novel FL-MOFs:Li₄?pdta??OC-NMe₂??CP-10?,Li₄?pdta??OC-NMe₂??H₂O??CP-11?,Li₄?pdta??CP-12?,Li₆?pdta?_1.5?DMP?_1.5?CP-13??DMP=1,3-dimethyl tetrahydro pyrimidin-2?1H?-one?and Li₅?pdta?_1.5?DMP?₃?H₂O?_0.5?CP-14?.CP-10 shows structural changes from 1D Spiral band to 3D accordion-pleats-like network.Temperature dependent structural changes have been monitored by Variable temperature single-crystal X-ray diffraction,which demonstrated that CP-10 exhibited large positive thermal expansion?PTE?behavior with?_V=163.7860MK^-1,mainly ascribed to the ultralight metal Li and the flexible-O-?CH₂?₃-O-functional moieties of V-shaped pdta linker.CP-11 shows similar layer structure to CP-10,however,the coordination of water molecule prevent the extension from 2D layer to 3D network.CP-12exhibits 3D network constructed from the butterfly-like Li₄ cluster and the FL of pdta.DMP was produced by the reaction in situ through the special solvothermal environment for the synthesis of CP-13 and CP-14.5.The thesis involved work has been systematically summarized,and some forward-looking work can be prospected in the subject.