With Nitrogen Impurity Aromatic Ring As The Ligand Synthesis And Properties Of New Type Coordination Compounds

For more than three decades the study on the magnetism ofmolecule-based compounds has been one of advanced disciplines in area ofmaterials science and it has mainly centred on the correlation factors betweenmagnetic coupling properties and its relevant structures for those magneticcompounds, in which relevant spin-carriers were bridged by sole atoms ormolecule, namely, the spin-carriers were connected by chemical bonds or themagnetic exchanges are through chemical bonds. Beside chemical bond theintermolecular force, such asππstacking and hydrogen bond, also play keyrole in magnetic interaction. But, papers that deal with the magnetic couplingthrough intermolecular force are very limited. This dissertation aims to search forsome factors that dominate magnetic coupling properties and to correlatemolecular force and its magnetic coupling properties. Based on this aspiration oraim two novel Cu^Ⅱcomplexes were synthesized, which include themono-nuclear complex [Cu（MP）Cl₂] （MP =3-Methylpyrazole-1,10-phenanthroline） （1） and the mono-nuclear complex[Cu（MP）Br₂] （2）. The infrared spectra characterization was made on the twocomplexes and their crystal structures were determined by X-ray diffraction. Thevariable-temperature （2-300 K） magnetic susceptibility measurement forcomplex （1） and complex （2） were performed and the fitting on the obtainedmagnetic data were made and the some experimental magnetic couplingproperties were obtained. In order to understand the correlation between themolecular forces and the relevant magnetic coupling properties, the theoreticalcalculations were performed. The calculations gave the information involving thespin density, the magnetic coupling sign and the magnetic coupling magnitudeof the relevant magnetic coupling pathways. From the information thecorrelation between the magnetic coupling properties and the relevant structuralfactors were explored and the some interesting results are obtained. Thisdissertation also involves the study on the magnetic coupling properties of complex [Co（PMP）（N₃）] （PMP = 2,9-bis（pyridin-2-methoxyl）-1,10-phenanthro-line）, in which its crystal structures has been reported. Based on theoreticalcalculations, the magnetic coupling properties that deal with its molecularforces were obtained.This dissertation also involves the syntheses and characterization of threenovel Cd^Ⅱcomplexes that have not been reported, namely, complex[Cd（KPP）₂Br（H₂O）]ClO₄H₂O （3） （KPP =2-（2-keto-pyridyl-1）-1,10-phenanthroline）, complex [Cd（TYP）（ONO）（H₂O）₂]- （TYP）（ClO₄） （4） （TYP=2-（1H-1,2,3-triazol-1-yl）-1,10-phenanthroline） andcomplex [Cd（DPP）（NCS）₂] （5） （DPP = [2,9-di（3,5-dimethyl-1H-pyrazol-1-yl）]-1,10-phenanthroline）.Based on the dissertation, the following intersting conclusions areobtained.1. The intermolecular force can indeed result in magnetic coupling.2. There occurred the spin delocalization on the Cu^Ⅱand Co^Ⅱ3d orbitalsto the relevant coordinated atoms in the studies systems.3. There is the spin delocalization and spin polarization in the studiedsystems.4. McConnell I spin polarization mechanism does not explain magneticcoupling sign for all magnetic coupling system dealing with intermolecular forcemagnetic coupling pathways.The obtained information in this dissertation may benefit to understand themagnetic coupling mechanism arisen from molecular force and it may alsobenefit to design and synthesize ideal molecule-based ferromagnet, especiallyfor those ferromagnet based on intermolecular force.