| From the 20th century,coordination chemistry has been flourished and makes an important contribution in atomic energy industry,nuclear fuel,rare metals,medical science and so on.Coordination chemistry can permeate into each branch of chemistry and biology.It has potential applications in chemical catalysis,medicine,magnetism,optics,and electrochemistry.Complex is composed of organic ligand and metal atom or ion through coordination bonds,including a coordination polymer and a discrete structure with mononuclear or finite polynuclear metal complex.Nowadays,constructing novel structures and functionalized complexes is one of the hot research directions of coordination chemistry.In this thesis,by the nucleophilic substitution reaction of halogenated hydrocarbons of 4'-bromomethyl-2-carboxylic acid methyl ester biphenyl with ethylamine,benzylamine,R-(+)-1-phenethylamine,nitrogen-containing dicarboxylic acid ligands with steric confinement,such as N,N-bis[4'-methylene-(1,1'-biphenyl)-2-carboxylicacid]ethylamine(H2L1),N,N-bis[4'-Methylene-(1,1'-biphenyl)-2-carboxylic acid]benzylamine(H2L2),R-N,N-bis[4'-methylene-(1,1'-biphenyl)-2-carboxylic acid]phenylethylamine(H2L3),have been prepared.These ligands were characterized by mass spectrometry and infrared spectroscopy.Under solvothermal method,15 metal complexes were synthesized by the reaction of these organic ligands with different transition metal ions.The main experimental task of this thesis is given below:(1)Synthesis and characterization of three nitrogen-containing dicarboxylic acid ligands as H2L1,H2L2 and H2L3.(2)Synthesis,characterization and magnetic properties of complexes 1-5:Complexes of the[Fe12(L1)6(CH3O)24](1),[Fe12(L2)6(CH3O)24](2)and[Fe12(L3)6(CH3O)24](3)with cycle structure were synthesized under solvothermal method by the reaction of FeCl3·6H2O with H2L1,H2L2 and H2L3.Furthermore,two Octahedron cobalt clusters of{[(Co2+)16(Co3+)4(?6-O)4(L)4(OCH3)12(?3-OH)12-(H2O)8](NO3-)8}(4)and{[(Co2+)16(Co3+)4(?6-O)4(L)4(?3-OH)20(OCH2CH3)4-(HOCH2CH3)8](NO3-)8}(5).They were characterized by powder X-ray diffraction,TGA,IR spectroscopy and their crystal structures were determined by single crystal diffraction.The magnetic properties of these complexes were also measured.(3)Synthesis and characterization of complexes 6-9 and the catalytic properties of complex 6 and 7:by the reaction of Cu(NO3)2·3H2O with H2L1,H2L3 or 4,4‘-bipy under solvothermal method,four tetra-nuclear copper complexes of{Cu4(L1)4[(CH3)2N]2(H2O)2}(6),[Cu4(L1)4(4,4-bipy)(H2O)2](7),{Cu4(L3)4[(CH3)3N](CH3OH)(DMF)2}(8),[Cu4(L3)4(4,4-bipy)(H2O)(DMF)](9)were synthesized and characterized by powder X-ray diffraction,TGA,IR spectroscopy.Their crystal structures were determined by single crystal diffraction methods.The catalytic property of complex 7 was explored under solvent-free condition at 25°C for Knoevenagel condensation reaction of benzaldehyde and malononitrile with the yield above 90%,showing that complex 7 has excellent catalytic activity.(4)Synthesis and characterization of complexes 10-15:by the reaction of H2L2,or H2L3 with Co(NO3)2·3H2O,Mn(NO3)2·3H2O and Zn(NO3)2·3H2O under solvothermal method,six one-dimensional chain complexes of{[Zn(L2)(DMA)]}n(10),{[Co(L2)(DMA)]}n(11),{[Mn(L2)(DMA)]}n(12),{[Co(L2)(CH3CH2O)]}n(13),{[Zn(L3)(DMA)]}n(14),{[Co(L3)(DMA)]}n(15).They were characterized by powder X-ray diffraction,TGA,IR spectroscopy and their crystal structures were determined by single crystal diffraction methods. |
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