Study On Syntheses,Crystal Structures And Magnetic Properties Of 3d/3d-2s Metal Complexes With Bis-(Salamo-type) Ligand

Salamo compounds,as derivatives of Salen compounds,are more stable than those of Salen compounds and have a variety of coordination modes.They are structurally diverse with s-,d-and f-orbital metal functional complexes.In recent years,Salamo-type functional complexes have shown unique properties and applications in optics,magnetism and catalysis.In this paper,monoxime compounds（2-[O-（1-ethoxyamine）]oxime-6-ethoxyphenol）were obtained by the [1 + 1] reaction of 1,2-diamine oxynitane and 3-methoxysalicylaldehyde,and then 2,3-dihydroxynaphthalene-1,4-dicarboxaldehyde was obtained by five steps chemical reaction.The Bis-（Salamo-type）open ring 18 crown 6 ligand H₄ L was synthesized by the [1 + 2] reaction of the dialdehyde with the above-synthesized monooxime compound and characterized by 1H NMR、13C NMR、high resolution mass spectrometry and IR.As a result of the two N2O2 sites and one open-ring 18-crown 6-site,it can react with transition metal ions and alkaline earth metal ions to prepare new kinds seven of homo/heteromultinuclear metal complexes,namely: [Co₃（L）（OAc）₂（CH₃OH）₂]·2CHCl₃（1）,[Co₂（L）Ca（OAc）₂]（2）,[Co₂（L）Sr（OAc）₂]（3）,[Co₂（L）Ba（OAc）₂（H₂O）]·2CH₃CH₂OH（4）,[Ni₂（L）Ca（OAc）₂（CH₃OH）₂]·2CH₂Cl₂（5）,[Ni₂（L）Sr（OAc）₂（CH₃OH）₂]·CH₃OH·CH₂Cl₂（6）and [Ni4（L）₂Ba2（OAc）4（CH₃OH）4（H₂O）₂]·CH₃OH（7）.The single crystal of seven metal complexes cultured by natural evaporation method was determined by X-ray single crystal diffractometer,and its chemical composition and spatial configuration were determined.The detailed crystallographic data were as follows:The seven metal complexes were characterized by X-ray single crystal diffractometer,and its chemical composition and spatial configuration were determined.Detailed crystallographic data are as follows:Co_mplex 1: Empirical formula,C₄₀H₄₄Cl₆N₄O₁6Co₃,Formula weight,1226.31,Monoclinic,P21/n,Unit call dimensions: a = 14.1780（12）?,b = 16.6498（14）?,c = 23.873（2）?,α = 90°,β = 100.520（9）°,γ = 90°,Z = 4,V = 5540.8（8）?3,R₁ = 0.0817,w R₂ = 0.1916.Co_mplex 2: Empirical formula,C₃₆H₃₄ Ca N₄O₁4Co₂,Formula weight,904.62,Triclinic,P-1,Unit call dimensions: a = 12.5293（11）?,b = 13.1610（19）?,c = 15.0421（17）?,α = 109.147（12）°,β = 103.296（9）°,γ = 100.181（9）°,Z = 2,V = 2192.9（5）?3,R₁ = 0.0555,w R₂ = 0.1150.Co_mplex 3: Empirical formula,C₃₆H₃₄ Sr N₄O₁4Co₂,Formula weight,952.16,Triclinic,P-1,Unit call dimensions: a = 12.5545（11）?,b = 13.2283（10）?,c = 15.0117（12）?,α = 109.370（7）°,β = 103.548（7）°,γ = 99.312（7）°,Z = 2,V = 2207.2 ?3,R₁ = 0.0616,w R₂ = 0.1678.Co_mplex 4: Empirical formula,C₄₀H₍48 Ba N₄O₁7Co₂,Formula weight,1112.02,Triclinic,P-1,Unit call dimensions: a = 10.2217（6）?,b = 13.551（8）?,c = 16.9476（10）?,α = 74.825（5）°,β = 79.515（5）°,γ = 81.710（5）°,Z = 2,V = 2216.1（2）?3,R₁ = 0.0569,w R₂ = 0.1097.Co_mplex 5: Empirical formula,C₄₀H₍46Cl₄ Ca N₄O₁6Ni₂,Formula weight,1138.09,Monoclinic,P21/n,Unit call dimensions: a = 15.4086（8）?,b = 12.0628（6）?,c = 29.5294（19）?,α = 90°,β = 100.627（5）°,γ = 90°,Z = 4,V = 5394.5（5）?3,R₁ = 0.1227,w R₂ = 0.3319.Co_mplex 6: Empirical formula,C₄₀H₍48Cl₂ Sr N₄O₁7Ni₂,Formula weight,1132.74,Orthorhombic,Pbcn,Unit call dimensions: a = 23.6620（5）?,b = 17.8187（5）?,c = 12.4666（3）?,α = 90°,β = 90°,γ = 90°,Z = 4,V = 5256.2（2）?3,R₁ = 0.0479,w R₂ = 0.0888.Co_mplex 7: Empirical formula,C₇₇H₉₂Ba₂N₈O35Ni4,Formula weight,2199.01,Monoclinic,P21/n,Unit call dimensions: a = 15.8005（3）?,b = 15.7041（3）?,c = 18.2762（4）?,α = 90°,β = 94.551（19）°,γ = 90°,Z = 4,V = 4520.62（16）?3,R₁ = 0.0426,w R₂ = 0.0826.These metal complexes were characterized by elemental analysis、 IR、 UV-vis spectra and XRD powder diffraction.The fluorescence properties and molecular magnetism were further explored.