Studies On The Construction,and Properties Of The MOFs Based On Dis(imidazole) Ligands

Metal-organic frameworks?MOFs?as a special material is widely applications in gas adsorption,ion recognition,bioactive probes,magnetism and organic catalysis.because of it has novel,changeable topology and different size pore configurations.It has opened up a new direction for the study of inorganic material chemistry and is favored by chemical researchers.From the point of view of the MOFs construct,?1?The strcuture of organic ligands.Nitrogen heterocyclic organic ligands with strong coordination ability and a variety of coordination modes were selected first.?2?Reaction system.The reaction temperature,material ratio,time,pH value,reaction solvent and other factors to achieve structural regulation.?3?Synthesis method.The main synthesis methods include solvent volatilization,solvothermal method,interfacial diffusion method,microwave method and so on.In this paper,a mixed strategy was used,with 3,6-bis?imidazol-1-yl?pyridazine?L¹?and3,6-bis?benzimidazol-1-yl?pyridazine?L²?as the main ligands.Twenty functional mixed metal organic complexes were synthesized under solvothermal conditions with different organic carboxylic acid molecules and transition metals.Then,the structures of complexes 1-20 were characterized by TGA,X-ray powder diffraction,IR,and X-ray single crystal diffraction.Finally,the spectroscopic performance,magnetic properties,and superelectrical properties of the corresponding complexes were discussed.The main points in this paper are summarized as follows:1.Using ligands L¹ and L² as the main ligand,five organic carboxylic acids?1,4-cyclohexanedioic acid=1,4-H₂CHDA,1,2,4-tricarboxybenzene=1,2,4-H₃BTC1,3,5-tricarboxybenzene=1,3,5-H₃----H₂OBA?is an auxiliary ligand,Six new metal organic complexes were synthesized under solvothermal conditions by combining d¹⁰ transition metal zinc cadmium:{[Cd?L¹??CHDA?]·H₂O}n?1?,[Zn₃?L¹?₂?1,2,4-BTC?₂?H₂O?₄]n?2?,[Zn?L²??D-CAM??H₂O?]_n?3?,[Zn₃?L²??1,2,4-BTC?₂?H₂O?₄]_n?4?,[Cd?L²??1,3,5-HBTC?]_n?5?and{[Zn?L²-BOA?]·H₂O}_n?6?.The purity,thermal decomposition resistance and unit cell structure of MOFs-1-6 were studied and discussed.The spectroscopic properties of MOFs-1-6and ligands were studied.2.Seven new metal-organic complexes have been synthesized based on L¹,L² and organic carboxylic acid auxiliary ligands reacted with Co?II?transition metal salt under solvothermalcondition,[Co?L¹??2,5-TDC??H₂O?]_n?7?,[Co?L¹??1,3-BDC?]_n?8?,[Co?L²?_0.5?1,4-BDC?]_n?9?,[Co₃?L²??1,2,4-TBC?₂?H₂O?₄]_n?10?,[Co_1.5?L²??1,2,4,5-HBTC??H₂O?₂]_n?11?,[Co?L²??5-AIPC?]_n?12??[Co?L²??1,4-NDC?]_n?13?.The electrode capacitance of the MOFs 7-13 was systematically studied.The electrode capacitance of the MOFs 7 can reach 291.35 F g^-1,and the electrode capacitance is reduced by27%after 2000 cycles,which has good cycle stability.Therefore,it can be applied to a capacitor as an electrode material.3.Seven new metal-organic complexes have been synthesized based on L² and organic carboxylic acid auxiliary ligands reacted with Ni?II?,Mn?II?and Cu?II?transition metal salt under solvothermal condition,[Ni?L²??2,5-TDC??H₂O?]_n?14?,[Ni?L²??1,3-BDC??H₂O?]_n?15?,[Ni?L²??1,4-BDC??H₂O?]_n?16?,[Mn?L²??2,5-TDC??H₂O?]_n?17?,[Mn?L²??2,6-PYDC??H₂O?]_n?18?,[Mn?L²??1,4-NDC?]_n?19??[Cu?L²??1,4-NDC?]_n?20?.The structure of the complexes14-20 was analyzed and discussed.It was found that the complex 14 was based on a three-dimensional interpenetrating three-dimensional framework,and the complex 15 was a six-connected new topology based on double interpenetration.16,19 and 20 are three-dimensional framework,the complex 17 is based on a three-dimensional adamantane configuration,and the complex 18 is a one-dimensional structure.Finally,the coordination mode of the organic ligands and magnetic properties in complexes 14-19 were studied.