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??,? = 90°,? = 100.520?9?°,? = 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??,? = 109.147?12?°,? = 103.296?9?°,? = 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??,? = 109.370?7?°,? = 103.548?7?°,? = 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??,? = 74.825?5?°,? = 79.515?5?°,? = 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??,? = 90°,? = 100.627?5?°,? = 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??,? = 90°,? = 90°,? = 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??,? = 90°,? = 94.551?19?°,? = 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.