Syntheses,crystal Structures And Spectral Properties Of Co(?),Ni(?),Cu(?) And Zn(?) Complexes With Half- And Single-salamo-type Ligands

Salamo-type compounds are derivatives of Salen-type compounds,which play an important role in the field of coordination chemistry.Compared with the Salen-type compounds,Salamo-type compounds have higher stability,and the hydrolysis and exchange reaction are not easy to occur in synthesis of Salamo-type metal complexes,and the Salamo-type complexes formed with transition metals have good application prospects in many fields.First of all,the oxime compounds,Half-Salamo-type ligand HL¹ was synthesized by the condensation reaction of the homemade 1,2-bis?aminooxy?ethane and 3-methoxysalicylaldehyde,purification and separation by column chromatography,and its four transition metal complexes have been successfully obtained: [Cu2?L1?2??-OAc?2]?1?,[{Ni?L1???2-OAc??OAc?}2Ni]·CHCl₃?2?,[{Zn?L1???2-OAc??OAc?}2Zn]·CHCl₃?3?and [Co4?L'?4?Me OH?4]?4?.The complexes 1₄ have been characterized by elemental analyses,IR and UV-Vis spectra and X-ray crystallography.Besides,the fluorescence properties,magnetic properties and antibacterial activities were also studied further.Then,the synthesis method of 4-methyl-7-hydroxy-8-formyl coumarin was optimized,and the suitable synthesis conditions and appropriate reaction steps were explored.Single-Salamo-type ligands with coumarin group have been prepared and purified,and the crystal growth conditions of the metal complexes have also been explored.The coumarin-containing single-Salamo-type ligands H₂L² and H₂L³ derived from the homemade 1,2-bis?aminooxy?ethane with 4-methyl-7-hydroxy-8-formyl coumarin were synthesized,and eight single crystals of transition metal complexes were successfully grown up: [Cu?L2??H2O?]?5?,[Cu?L3?]·CHCl₃?6?,[Co?L3??Me OH?]·CHCl₃?7?,[{Co2?L3??Me OH??m2-OAc?}2Co] 3CH2Cl2?8?,[{Ni L3?Me OH???2-OAc?}2Ni]·4CH2Cl2?9?,[{Ni?L3??Me OH??Ph COO?}2Ni]?10?,[Zn?L3??Me OH?]·CH2Cl2?11?and [Zn?L3??Et OH?]?12?.The complexes 5₁2 have been characterized by elemental analyses,IR and UV-Vis spectra and X-ray crystallography.In addition,the synthesis methods,solvents effects,anionic effects,supramolecular interactions and fluorescence properties of the complexes 5₁2 were also studied.Detailed crystallographic data are as follows:Complex 1: C₂₄H₃₂Cu₂N₄O₁₂,Formula weight,695.61,Monoclinic,P2₁/c;Complex 2: C₂₉H₃₉Cl₃N₄Ni₃O₁₆,Formula weight,982.12,Triclinic,P-1;Complex 3: C₂₉H₃₉Cl₃N₄O₁₆Zn₃,Formula weight,1002.16,Triclinic,P-1;Complex 4: C₄₄H₆₀Co₄N₄O₂₀,Formula weight,1200.68,Triclinic,P-1;Complex 5: C₂₁H₂₀CuN₂O₈,Formula weight,491.93,Triclinic,P-1;Complex 6: C₂₅H₁₉Cl₃CuN₂O₈,Formula weight,645.31,Monoclinic,P2₁/c;Complex 7: C₂₆H₂₃Cl₃CoN₂O₉,Formula weight,672.74,Monoclinic,P2₁/c;Complex 8: C₅₇H₅₆Cl₆Co₃N₄O₂₂,Formula weight,1538.54,Triclinic,P-1;Complex 9: C₅₈H₅₈Cl₈N-4Ni₃O₂₂,Formula weight,1622.81,Triclinic,P-1;Complex 10: C₆₄H₅₄N₄Ni₃O₂₂,Formula weight,1407.24,Triclinic,P-1 Complex 11: C₂₆H₂₄Cl₂N₂O₉ Zn,Formula weight,644.74,Monoclinic,P2₁/c;Complex 12: C₂₆H₂₄N₂O₉Zn,Formula weight,573.84,Monoclinic,P2₁/n.