Syntheses,Structures And Properties Of Metal Complexes Based On Naphthalene Oxime And Hydroxamic Acid

The controlled self-assembly of supramolecular structures can be achieved through rational ligand design and by the appropriate choice of metal ions and reaction conditions.Research into coordination-based self-assembly processes has yielded a vast array of compounds with novel structural topologies,physical propery ties,and molecular recognition behavior.Hydroxamic acid and oxime are the main ligands for synthetic mrtal crown ethers because of their?N,O? atoms which are easily coordinated to metal ions.Therefore,in this paper,oxime and hydroxamic acid ligand containing a naphthalene were obtained byreaction with different metal salts.The structure were characterized by elemental analisis,infrared spectroscopy,and X-ray single crystal diffraction.The main sections is as follows:1.The reactions of 3-hydroxy-2-naphthoyl hydroxamic acid ligand?L₁? with manganese salt and rare earth salt to obtain 4 metal complexes:[Na₃?Mn^??₄?Mn^??₁₈O₈?L₁?₁₂?O₂CMe?₁₈?Cl?6]·6H₂O?1?,,NaDy^??OAc?₄[12-MC_Mn^??N?nap-4]·4H₂O?2?,NaGd^??OAc?₄[12-MC_Mn^??N?nap-4]·4H₂O?3?,NaEu^??OAc?₄[12-MC_Mn^??N?nap-4]·4H₂O?4?.Complexes 1 are isostructural and have a novel[Mn22] structure botained by linking two[Mn11] group via a central Na ion through ligand naphthol hydroxyl oxygen atoms.Each[Mn11] contains cleven manganese ions,and each three Mn^? form a triangle type,which is connected to the farther Mn^? through the oxygen and nitrogen atoms of the ligand hydroxy oxygen and sulfhydryl groups and two Mn^? are respectively located at the center on the axis of triangle.Magnetic studies have shown that all metal ions exhibit antiferromagnetic coupling.Complexes 3-5 are metal crown ethers of NaLn[12-MC-4],and the central rare earth atoms are connected via a oxime oxygen aotm on the ligand.The metal ions in the complex 2-4 molecules are antiferromagnetic.2.The reactions of 2-hydroxy-1-napthaldoxime ligand?L₂? with manganese salt and cobalt salt to obtain four metal complexes:[Mn₆O₂?L₂?₆?O₂CMe?₂]·2H₂O·2DMF?5?,[Mn₆O₂?L₂?₆?O₂PhMe?₂?MeOH?₄]?6?,[Mn₆O₂?L₂?₆?Cl?₂?EtOH?₆]?7?,[Co₂?L₂?₂N₃Py₄]ClO₄?8?.The structure was determined by a series of characterization methods.The complexes 5-7 are all hexagonal manganese metal crown ethers,and the ligands removed two protons through the naphthalene hydroxy oxygen aotms and the sulfhydryl nitrogen,oxygen atoms and manganese forming a 9-MC-3 unit.Two units are connected to manganese ions in another strucyural unit through a sulfhydryl oxygen atoms.The coordination configuration of manganese ions is a distorted octahedron.The metal ions exhibit antiferromagnetic coupling and magnetic relaxation phenomenon,showing the behavior of single-molecule mangnets.Complex8 is a dinuclear cobat complex and the cobalt ion in the molecule is calculated to be+3 valence,and both cobalt ions are octahedral coordination configuration with six coordination distortions.3.The reactions of 2-hydroxy-1-napthalenone oxime ligand?L₃? with manganese salt and iron salt to obtain four metal complexes:[[Fe₆^?O₂?naphthsao?₄?O₂CPh?₆]?9?,[Mn₄^??L₃?₄?HL₃?₄?10?,[Mn₉O₄?L₃?₆?MeO?₃?O₂CPh?₄?EtOH?₅]?11?,[Mn₉O₄?L₃?₆?MeO?₃?H₂O?₉]?12?.The structure was determined by a series of characterization methods.Complex 9 is a complex of six-core iron with antiferromagnetic coupling between iron ions.Complex 10 is a tetranuclear manganese complex.Four manganese ions form a cubic alkane structure through a oxime oxygen atom.The valence of manganese is+3,and the manganese ions exhibit the antiferromagnetic interaction.There is a single-molecule magnet behavior under the 1000 Oe field.Complex 11 is a double layered metal crown ether with an upper layer of 9-MC-3 metal crown and alower layer of 15-MC-6 metal crown ether,joined by the hydroxyl oxygen atom and oxime oxygen aotm.The complex exhibits a single molecule magnet behavior at zero field.The structure of the metal complex 12 is similar to that of the complex 11 except the anionic small ligand attrached to the manganese ion is different.