Synthesis,Structure And Properties Of 3d/3d-4f Polynuclear Metal Clusters

Polynuclear metal complexes are enjoying widespread current interest not only because of their nanoscale and aesthetically pleasing molecular structures but also of their interesting luminescent,electronic,magnetic,and catalytic properties.Recently,with the development of supramolecular chemistry,the large number of polynuclear metal cluster shaped with globular,ladder,tube and spiral have been eported,however,these synthesized which mostly by chance,thus the rational design and synthesis the polynuclear metal clusters with specific structures and functions are still facing a huge challenge.This thesis was divided into four parts,which including the brief introduction of the general research situation of polynuclear metal clusters and a preliminary studying of the synthesis,structure and properties of three series clusters.The first chapter,the overview have been made system of polynuclear metal clusters including its characteristics,applications and researching progress,and the general research way of this subject was also introduce briefly.In the second chapter,four complexes(1)?(4)have been synthsized based on frustrated triangular Fe3?3O with rare-earth metal ions by controlling the pH.[Dy2Fe6(?3-OH)6(?4-O)3(PhCOO)9(DMF)6](OH)3(1)[Gd2Fe6(?3-OH)6(?4-O)3(PhCOO)9(DMF)6](OH)3(2)[Sm2Fe6(?3-OH)6(?4-O)3(PhCOO)9(DMF)6](OH)3(3)[Ce2Fe6(?3-OH)6(?4-O)3(PhCOO)9(DMF)6](OH)3(4)Single crystal X-Ray diffraction structural analysis indicated that the four complexes were homeomorphism,all like a brass cymbal.Magnetic analysis indicated that complex(1)and complex(3)exhibited anti-ferromagnetic properties in the temperature range of 300-2.OK,while complex(4)exhibited ferromagnetic properties.In the third chapter,four complexes(5)?(8)have been synthsized based on frustrated triangular Fe3?3O with rare-earth metal ions metal ions by controlling the pH under hydrothermal condition.[Dy4Fe12(?3-O)4(?4-O)6(?3-OH)4(PhCOO)24](DMF)(H2O)(5)[Gd4Fe12(?3-O)4(?4-O)6(?3-OH)4(PhCOO)24](DMF)(H2O)(6)[Sm4Fe12(?3-O)4(?4-O)6(?3-OH)4(PhCOO)24](DMF)(H2O)(7)[Pr4Fe12(?3-O)4(?4-O)6(?3-OH)4(PhCOO)24](DMF)(H2O)(8)Single crystal X-Ray diffraction structural analysis indicated that complexes(5)-(8)were homeomorphism.Their structure consisted of two flat[Fe4?(?3-O)2(PhCOO)5]base units,the two units connected by rare earth ions and oxygen atoms in the middle,at both ends by two Fe3+and?3-O2-links,resulting a new units Ln4Fe8.Magnetic analysis indicates that complex(5)-(7)exhibited anti-ferromagnetic properties in the temperature range of 300-2.OK,while complex(8)exhibited ferromagnetic properties.In the fourth chapter,complexes(9)?(12)have been synthsized based on ligand 6,6'-(hydrazine-1,2-diylbis(methylene))bis(2-methoxyphenol)(H2L)with rare-earth metal ions and transition metal ions and characterized their properties completely.[Ni4L2(O2CCMe3)4DMF2](9)[Zn4L2(Ac)2(MeO)2](10)[Ni2Gd2(L)2(NO3)4(O2CCMe3)2(DMF)2](11)[Ni2Dy2(L)2(NO3)2(O2CCMe3)4(DMF)2](12)The structure of complex(9)like a sandwich,four Ni2+in middle,two ligands in the up and down sides.What was unlike complex(9),the four Zn of complex(10)were coordinated with four phenol oxygen of two ligands,two O of methanol resulting in a tetranuclear based on "chair"structure.Complexe(11)and Complexe(12)were homeomorphism,which structures like complex(9).Magnetic indicated that complex(11)and(12)exhibited anti-ferromagnetic properties.