Synthesis And Properties Of Complexes Constructed By Simple Bridging Ligands

In recent years,coordination compounds with novel structures and excellent properties had synthesized by using coordination bonds and various supramolecular forces(e.g.H-bonds,?-?stacking,van der Waals interaction,hydrophobic lipophilic interaction,electrostatic interaction,etc.),and researching the relationship between its structure and properties had become the focus of coordination chemistry.Based on its chemical sensing,luminescent and magnetic properties,compounds may be widely applied in non-linear optical materials and magnetic materials.In this work,we synthesized 8 cases of compounds by microwave assisted solvent synthesis and hydrothermal synthesis using several simple bridging ligands(formate,acetate,azido,5-methyltetrazolium,8-hq).The coordination mode,optics properties and magnetic properties has been described.The main results are as follows:1.Four kinds of super-perovskite structured 3D metal formate compounds([Ba₄Mn₃(HCO₂)₁₃]_n(1);[Ba₄Co₃(HCO₂)₁₃]_n(2);[Ba₄Mg₃(HCO₂)₁₃]_n(3);[Ba₄Fe₃(HCO₂)₁₃]_n(4))were synthesized by microwave-assisted solvothermal synthesis with formate as bridging ligands.Compounds 1-4 are isomorphous structure with noncentral symmetry,the nonlinear optical test results of complexes 1 and 2 exhibits second-harmonic generation(SHG)response of approximately 0.32 and 0.28 times of KDP(KH₂PO₄),respectively.Magnetic properties indicated Mn ions in compound 1 was an antiferromagnetic coupling,Co ions in compound 3was an antiferromagnetic coupling,T_C=4.5K was determined by FCM and ZFCM,the existence of spontaneous order was confirmed.2.A metal acetate cluster([Fe₃O(CH₃CO₂H)₃(CH₃CO₂)₆]Fe Cl₄(5))was synthesized by hydrothermal synthesis by acetate as bridging ligands.The structure of compound 5 was determined at different temperatures(170K,423K),and it was indicated that with the increase of temperature,there are phase transitions caused by the rotation of Fe Cl₄ radicals.High temperature magnetic properties indicated the magnetic properties of the complex were not affected by phase transition.3.Three kinds of cluster([Co₁₂(L¹)₃(L²)₆(N₃)₃](6);[Ni₆Na(L)₁₂](7)and[Ni₆Na(L)₁₂](8))were synthesized by hydrothermal synthesis by azido,5-methyltetrazolium and 8-hq,HL=8-hq,HL¹=5-methyltetrazolium,H₂L²=7,7,-(ethane-1,1,-diyl)8-hydroxyquinoline,H₂L²was generated by in situ reaction of ligand HL and ethanol.Magnetic properties indicated that Co ions in compound 6 is an antiferromagnetic coupling,Ni ions in compound 7is an antiferromagnetic coupling,Ni ions in compound 8 is a ferromagnetic coupling,it could be spin glass.