Synthesis, Structure And Properties Of Transition-metal Coordination Compounds With O-containing Ligands

Over the last decades, the field of coordination compounds had been developingrapidly. Due to their structural diversity and potential applications in the optical,electrical, magnetic, and catalytic, gas adsorption and separation, the design, synthesisof coordination compounds has been widespread concern. Usually the synthesisprocess of the coordination compounds is very complex, and there is no systematicand theoretical explanation for the reaction mechanism. It requires extensiveexperiments and in-depth analysis to realize the ultimate target of directional designand synthesis of coordination compounds.This thesis used different organic ligands and obtained11coordinationcompounds. The corresponding structure and properties have been studied.（1） Three coordination compounds have been prepared with the flexible ligands（oba or pda）. Co₂（oba）₂（H₂O）₄（DMF）（1）, Cu（oba）（DMF）（H₂O）（2）, Cu（pda）（DMF）（3）. Compound1and3present a2D structure while compound2present a3Dstructure. Moreover, the layers in compound1are interpenetrating. Compound2exhibits a triple interpenetrating structure.（2） Two acidic imidazolium-based ligand L1, L2were prepared from L-alanineand glycine. Using them, we prepared two2D coordination compounds undersolvothermal environment, Cd（L1）₂（4） and Zn（L2）₂（5）. In compound4the Cd2+centers are in irregular octahedral geometry and extend to a2D structure through theligand L1, and the chiral moieties on the ligand are partially racemized; compound5also display a two-dimensional layer structure, and the Zn2+ions are in tetrahedral geometry. No chiral character exists in compound5.（3） With the predesigned versatile quinquedentate Schiff base ligand（2-hydroxy-3-methoxyphenyl）-N, N, N-tris （hydroxymethyl）methanideaminium（H₄L3）, we obtained four Fe-Ln based heteronuclear compoundsNaFe4LnO（H₂L₃）₂（HL3）（O2CPh）₄（CH₃O）（NO₃）₂（Ln=La（6）, Gd（7）, Dy（8）, Lu（9））,two1D compounds Mn₃（H₂L₃）₂（N₃）₂（CH₃OH）₂·2CH₃OH （10） andNaCo₂（H₂L₃）₂（N₃）₄·CH₃OH （11）. Their structures and magnetic properties wereinvestigated. Magnetic measurements indicated that the paramagnetic centers areantiferromagetic coupled in the four Fe-Ln based heteronuclear compounds, whilecompound [Mn₃（H₂L₃）₂（N₃）₂（CH₃OH）₂·2CH₃OH] display intrachain ferromagneticinteraction and interchain antiferromagnetic interaction. Compound[NaCo₂（H₂L₃）₂（N₃）₄·CH₃OH] is diamagnetic since the Co³⁺ions are in low-spin state.