Phenanthroline And Its Derivatives For The Synthesis And Properties Of A New Ligand Complexes

In this dissertation ten novel coordination complexes have been designed and synthesized, and the ten complexes include the two-dimensional Ni(II) coordination polymer [Ni(μ_1,3-SCN)(μ-ophen)(CH₃OH)]_n (1) with 2-deprotonated-hydroxyl-1,10-phe- nanthroline and thiocyanate as mixed bridge ligands; binuclear Fe(III) complex [Fe₂(μ-O)(phenpy)(H₂O)₂(NO₃)₂]₂(NO₃) (2) with oxygen ion as bridge ligand and 2-(2-keto-pyridyl-1)-1,10-phenanthroline (phenpy) as terminal ligand; binuclear Cd(II) complex, [Cd₂(μ-phenpy)₂(phenpy)₂(H₂O)₂] (3), with 2-(2-keto-pyridyl-1)-1,10-phenanth roline as bridge ligand and terminal ligand; binuclear Zn(II) complex, [Zn₂(μ-N₃)₂(N₃)₂(phenpy)₂] (4) with azide as bridge ligand and 2-(2-keto-pyridyl-1)- 1,10-phenanthroline as terminal ligand; and the mono-nuclear complexes: [Zn(phenpy)₂(ClO₄)₄][ClO₄] (5), [Ni(phenpy)₂(ClO₄)₄][ClO₄] (6), [Co(phenpy)₂(ClO₄)₄] [ClO₄] (7), [Co(phenpy)(Cl)₂] (8), [Cd(phenpy)(Cl)₂] (9) and 2-deprotonated-hydroxyl-1,10 -phenanthroline as terminal ligand; and the mono-nuclear complexes: [Ni(phenpy)₂(H₂O) ₂](NO₃) (10)。The ten complexes were characterized by infrared spectra, elemental analysis and X-ray crystallographic analysis. The variable-temperature magnetic susceptibilities for complex (1) and (2) were measured at 2-300 K, and for complex (1) a binuclear Ni(II) fitting formula was used and the fitting gave the magnetic coupling constant 2J = -0.668 cm^-1. For complex (2) the fitting on the susceptibilities above 55 K was conducted by a binuclear Fe(III) fitting formula, and the magnetic constant 2J = -157.51 cm^-1 was obtained, and at the same time complex (2) displays spin canting property at low temperature. The fluorescent spectra were measured for complexes (3) and (4), and the structure-property was studied for these complexes dealing with their fluorescent properties, in which complex (3) and (4) exhibits the closely related property between its structure and the fluorescence.The special advantages and contributions of this dissertation are as follows.1. A series of novel complexes with 2-(2-keto-pyridyl-1)-1,10-phenanthroline as ligand have been synthesized, which has not been reported as yet. 2. The magnetic coupling mechanism was studied for a two-dimensional Ni(II) coordination polymer with mixed bridged ligands.3. The spin-canting property was observed for a binuclear Fe(III) complex for the first time.4. The closely related structure-fluorescence specialty was observed at a binuclear Cd(II) complex.The results of this dissertation will benefit the synthesis of ideal molecular-magnets and it also benefits the understanding for bio-function of bridged metallic ions in metallic proteins. The results of this dissertation also will benefit the synthesis of ideal fluorescent materials.