Syntheses,structures And Properties Of Metal Complexes Based On Quinoline Hydroxamic Acid And Quinoline Oxime

Quinoline Oximes and quinoline hydroxamic acids with monohydroxyl and dihydroxy can chelate with different metal ions to form polynuclear complexes.The ligands play an important role as a template in the reactions.It is easy to form a metallacrown with a certain size,and it can also form a variety of complexes with different transition metals or rare earth-transition metals.In this thesis,we through quinoline-2-hydroxamic acid and quinoline aldoxime ligands with different transition metal salts,15 complexes were synthesized under different synthesis environments.They were characterized by X-ray diffraction single-crystal,FT-IR spectra,elemental analyses,X-ray diffractometer to characterize the complexes,and the near-infrared fluorescence and magnetic property measuring instrument was used to study the properties of fluorescence and magnetism.1.Five transition metal complexes with the metallacrown structure was successfully synthesized by using quinoline-2-hydroxamic acid as the main ligand:[Na Ni₅(quinha)₅(py)₁₀(H₂O)₂]·OTf(1),[Ni₆(quinha)₅(py)₁₀(OH)(H₂O)]·OTf(2),[Ni₆(quinha)₆(py)₁₂](3),[Co₅(quinha)₅(py)₁₀](4),[Zn₅(quinha)₄(py)₅](Cl O₄)(SCN)(5).Analyzing the crystal structures of the complexes 1-5.Complexe 1 is a 15-MC-5metallacrown which chelates one sodium cation in the center,and one trifluoromethanesulfonate anion is on the outside of the metallacrown.Complexes 2-3 are18-MC-6 and 15-MC-5 nickel metallacrown respectively.Complex 4 is a 15-MC-5metallacrown of pentaconuclear cobalt and complexes 5 is a 12-MC-4 metallacrown of pentaconuclear zinc.The magnetic properties of complexes 2 and 4 were studied,the complex 4 exhibit single molecular magnet behavior and the maximum peak value can not be observed in the applied 1000 Oe Dc field.Complex 5 showed a weak fluorescence peak at 615.0 nm,and the fluorescent properties of complex 5 were studied.2.Seven complexes were successfully synthesized by using quinoline-2-hydroxamic acid as the main ligands:[Ln₂Ni₄(quinha)₆(py)₈(OAc)₂(H₂O)₂],[Ln=Er³⁺,Lu³⁺,Sm³⁺,Eu³⁺,Gd³⁺,Tb³⁺,Dy³⁺(1),Dy³⁺(2)].Complexes 6-12 have a[Ln₂Ni₄]crystal framework.The difference of complexes 6-7 were that the coordination mode of Dy ion and acetate.The measurement of susceptibility and the measurement of AC magnetic susceptibility under an applied DC field of 1000 Oe and that complexes 6-7 have exhibited slow relaxation behavior.3.Those metal complexes were successfully synthesized by using the quinoline-2-formaldehydeoximeasthemainligand:{[Ni₅(qcah)₇(Hqcah)(CH₃OH)(SCN)(OH)]Cl O₄}(13),[Ni₄(qcah)₄(N₃)₄Py₄](14),[Co₂(qcah)₂(Hqcah)₂(OCH₃)]SCN(15).Complex 13 is a pentanuclear nickel metallacrown and“fused”9-MC-3 metallacrown structure.Complex 14 is a 12-MC-4 metallacrown of12-MC-4,and complex 15 is a dinuclear cobalt compound.Magnetic measurement reveals that the complexes 13-14 have weak antiferromagnetic interaction in the temperature range of 50.0K-300.0 K.A frequency-dependent out-of-phase signal was found in complex 15,which suggests that the complex 15 exhibited single molecular magnet behavior.