Studies On The Synthesis,Structure And Properties Of Complexes Of Cyclic Imide Derivatives Ligand

The metal complexes of cyclic imide derivatives have aroused great interest because of their potential applications as functional materials in the areas of magnetism,electrochemistry,luminescence and energy storage.In this thesis,Nhydroxy-1,8-naphthalimide was chosen as ligand to prepare complexes with different kinds of metal ions,giving fifteen unreported metal complexes which include three transition metal complexes,three Ni(?)polymers and nine rare earth metal complexes.They were characterized by infrared spectroscopy,elemental analysis,X-ray powder diffraction analysis and single crystal X-ray diffraction analysis.The thermostability and magnetic properties of some complexes were also investigated.The main work is presented below:1.The reaction of N-hydroxy-1,8-naphthalimide(HL)with Co(OAc)2·4H2O gave a discrete tetranuclear complex[Co4(L)4(CH3COO)4](1),in which the four Co(?)ions are six-coordinated in distorted octahedral geometries.In complex(1),all of the ligands L-adopt ?2:?4-bridging modes connecting two Co(?)ions,which leads to the formation of a parallelogram skeleton for the four Co(?)ions.The reaction of HL with Ni(NO3)2·6H2O in the presence of 2,2'-bpy gave a mononuclear Ni(?)complex[Ni(L)2(2,2'-bpy)]·5H2O(2).The Ni(?)ion in complex(2),which is sixcoordinated in distorted octahedral geometries,is chelated by the L-and 2,2'-bpy ligands to form a simple mononuclear skeleton.The reaction of HL with NiC12-6H2O gave a trinuclear complex[Ni3(L)3Cl3(H2O)3](3).The three Ni(?)ions in complex(3)are six-coordinated in similar coordination environments.All L-ligands in complex(3)adopt ?2:?4-bridging modes to connect three Ni(?)ions,leading to the formation of a planar triangular skeleton.Their magnetic studies indicate the presence of dominant antiferromagnetic interactions in complex(1)and(3).2.Complexes[Ni(L)(HCOO)(H20)]n(4),[Ni(L)2(4,4'-bpy)]n(5)and[Ni(L)(HCOO)(4,4'-bpy)]n(6)were separated from the reactions of N-hydroxy-1,8naphthalimide(HL)with Ni(NO3)2·6H2O in different conditions,respectively.Complex(4)has one-dimensional linear chain structure formed from connection of Ni(?)ions by the hydroxy oxygen atom of L-ligands.The[Ni(L)2]units in complex(5)are bridged by 4,4'-bpy moleucles to form a one-dimensional linear chain.The Ni(?)ions in complex(6)were cross-linked by 4,4'-bpy and HCOO-ligands,constructing a two-dimensional structure.The Ni(?)ions in complexes(4)-(6)are all six-coordinated.Their magnetic studies indicate the presence of dominant antiferromagnetic interactions between the metal ions of these complexes.3.The reactions of N-hydroxy-1,8-naphthalimide(HL)with Ln(NO3)3·xH2O gave a series of dinuclear compounds:[Tb2(L)4(NO3)2(CH3OH)2]·H2O(7)and[Ln2(L)2(N03)4(DMF)2][Ln=Dy(8),Ho(9),Er(10)].Each Ln(?)ions in these high-symmetrical complexes are nine-coordinated.The reactions of HL with LnCl3·6H2O yielded a series of pentanuclear compounds:[Ln5(L)6(?3OH)3Cl2(CH30)(H20)6]C13,2CH2C12·16H2O[Ln=Gd(11),Tb(12),Dy(13),Ho(14),Er(15)].Their skeletons show a chair-like appearance.In complexes(11)-(15),the five Ln(?)ions are in different coordination environments,and all L-ligands adopt?2:?4-bridging modes connecting five Ln(?)ions.The variable-temperature solid state magnetic susceptibilities measurements of complexes(7),(9)and(10)-(15)indicate the presence of dominant antiferromagnetic interactions between their metal ions.Compound(8)presents ferromagnetic exchange interaction between Dy(?)ions.Alternating current susceptibility data indicate that only the complex(8)shows single-molecule magnetism behavior.