Studies On The Synthesis,Structure And Properties Of Transition Metal Complexes Of Aromatic Oxime

In recent years,polynuclear clusters have attracted much interest in chemistry.To construct novel clusters bearing aesthetical structures and aimed properties is becoming hot topics,which leads to its full development in fields such as biological activity,catalysis and magnetic properties.In this thesis,indane-1,2,3-trione dioxime are used as ligands to react with different metal salts by solvothermal method and conventional solution method,giving one cluster with trigonal prismatic skeleton,five compounds containing planar cluster,and three cluster-based two-dimensional compounds.They were structurally determined by single crystal X-ray diffractional analysis,powder X-ray diffractional analysis and infrared spectroscopy.Their thermal stabilities and magnetic properties were also studied.The main work is presented below:1.[(CH3)2NH2][Fe6L6(μ3-O)2(μ2-OH)3(CH3OH)3]·10H2O·4CH3OH(1),[Fe3L3(μ3-O)(H2O)3Cl]-2DMF-4H2O(2)and[Fe3Na3(L)6(μ3-O)(H2O)10]n·9nH2O(3)were separated from the reactions of indane-l,2,3-trione dioxime with FeCl3·6H2O.Complex(1)presents trigonal prismatic Fe6 skeleton.The six Fe(Ⅲ)ions are divided into two layers.The three Fe(Ⅲ)ions in each layer are consolidated by one μ3-O2-to a planar triangular Fe3 unit.The two Fe3 units are further linked by μ2-OH-and CH3OH to build the Fe6 skeleton.Complex(2)is a discrete planar trinuclear complex with two Fe(Ⅲ)ions six-coordinated and the other one five-coordinated.The three Fe(Ⅲ)ions in complex(2)are consolidated by one μ3-O2-ion and three oxime ligands to form an equilateral triangular skeleton.Complex(3)features linear trinuclear Fe3 secondary building units,which are bridged by Na+ through ligands to form a two-dimensional structure.The Na(I)and Fe(Ⅲ)ions in(3)are all six-coordinated.The magnetic studies of complex(1)and(2)indicate the presence of antiferromagnetic interactions between their metal ions.2.[Ni4L2(HL)2(py)4][Er(NO3)5]·4THF(4)and[Ni4L4(py)4]·2C5H5N·CH3OH(5)were separated from the reactions of indane-1,2-trione dioxim with Ni(OAc)2 and Er(NO3)3 or just with Ni(NO3)2,respectively.Complex(4)crystallizes in the triclinic space group C2c,while complex(5)crystallizes in the orthorhombic space group Pnnm.They contain similar Ni4 unit.The difference between(4)and(5)is that(4)has a[Er(NO3)3]2-anion which is not found in(5).The Ni(Ⅱ)ions in both compounds are six-coordinated in distorted octahedral geometries.The magnetic studies of complex(4)indicate the presence of anti ferromagnetic interaction between the metal ions.3.[Mn6Na3L6(μ3-OH)2(CH3COO)6]nOH·2C2H5OH·6H2O(6),[Mn3Na2L3(μ3-O)(CH3COO)3(C2H5OH)2(H2O)(THF)]n·2THF(7),[Mn3L3(μ3-O)(H2O)4(CH3COO)]·H2L·9H2O(8)and[Mn3L3(μ3-O)(CH3COO)(py)3(C2H5OH)]-2THF(9)were separated from the reactions of indane-1,2,3-trione dioxime with Mn(OAc)2 by controlling different reaction conditions.Complex(6)crystallizes in the monoclinic space group R-3 and the othe other three compounds crystallizes in the triclinic space group Pi.Complex(6)and(7)have similar planar triangular Mn3 secondary building units,which are linked by Na+ through ligands to two-dimensional frameworks with different topologies.Complexes(8)and(9)show similar planar triangular Mn3 skeletons,in which the three Mn(Ⅲ)ions in are consolidated by one μ3-O2-ion and three oxime ligands to form an equilateral triangular skeleton.The difference between complexes(8)and(9)is that their axial ligands are different.Their magnetic studies revealed the presence of ferromagnetic interaction between the metal ions in complex(6)and the presence of antiferromagnetic interactions between the metal ions in the other three compounds.