1, 10 - Brown's Lin Derivatives As Ligand And Synthesis Of Coordination Compounds And Their Properties

For more than three decades the study on the magnetism of molecule-basedcompounds has been one of advanced disciplines in area of magneticchemistry 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 ormulti-atoms molecule, namely, the spin-carriers were connected by chemicalbonds or the magnetic exchanges are through chemical bonds. Besidechemical bond the intermolecular force, especiallyπ-πstacking and hydrogenbond, also play a key role in molecular magnetic interaction, but papers thatdeal with the magnetic coupling through intermolecular force are very limited.This dissertation aims to search for the factors between magnetic interactionand the intermolecular force.Derivatives of 1,10-phenanthroline play an important role in moderncoordination chemistry. In this dissertation，five kinds of derivatives of 1,10-phenanthroline have been synthesized, and ten novel metal complexes havebeen prepared with the five compounds as ligands, namely, one-dimensionalCu^Ⅱchain complex {[Cu（μ-L₁）（H₂O）Br]（H₂O）}n（1） （L₁=2-hydroxy-1,10-phenanthroline） with 2-hydroxy-1,10-phenanthroline asbridged ligand、binuclear Cu^Ⅱcomplex [Cu₂(μ_1,3-SCN)₂（L₁）2（H₂O）₂] （2） andmononuclear Cu^Ⅱcomplex [Cu（L₁）2（H₂O）]（CH₃CN）（H₂O）4（3） with2-hydroxy-1,10-phenanthroline as capped ligand; mononuclear MnIIcomplex[Mn（L₂）₂（H₂O）₂)]（H₂O）（NO₃） （4） （L₂= 2-（methyl-1H-imidazol-1-yl）-phenanthroline） with 2-（methyl-1H-imidazol-1-yl）-phenanthroline as terminal ligand; mononuclear Cu^Ⅱcomplex [Cu（L₃）（OHCH₃）（SO4）]（CH₃OH） （5） （L₃=N,N-dimethyl-1,10-phenanthrolin-2-amine） with N,N-dimethyl-1,10-phenanthrolin-2-amine as ligand; one-dimenstional Mn^Ⅱchain complex {[Mn（L₄）2（μ（1,3）-N₃）]（ClO₄）}n（6）、mononuclear Mn^Ⅱcomplex[Mn（SCN）₂（L₄）₂] （7）、mononuclear Mn^Ⅱcomplex[Co（NCS）2（L₄）2] （8）andmononuclear Zn^Ⅱcomplex [Zn（NCS）（L₄）₂][Zn（NCS）₃（L₄）] （9） （L₄=2-chloro-1,10-phenanthroline）, in the four complexes2-chloro-1,10-phenanthroline functions as terminal ligand; mononuclear CuIcomplex [Cu（L₅）(μ_1,3-SCN)]_n（10） （L₅=2-（1,2,3-1H-triazol-1-yl）-1,10-phenanthroline） with2-（1,2,3-1H-triazol-1-yl）-1,10-phenanthroline as terminal ligand. The tencomplexes were characterized with infrared spectra and their single crystalstructures were determined by X-ray diffraction.The variable-temperature （2.00-300 K） magnetic susceptibility measurementfor complexes （1）、（2）、（6） and （7） was performed and the magnetic couplingmagnitudes for these complexes were obtained by fitting for the data of themagnetic susceptibility. The theoretical calculations were performed oncomplex （2） and （5） and the calculations gave the relevant information dealingwith the spin density and the magnetic coupling strengths. Based on theinformation of the crystal structures and the relevant magnetic couplingstrengths, the relevant magnetic coupling properties from the molecular forces,such asπ-πstacking and hydrogen bonds, were studied and the somecorrelation factors of structure-magnetism property have been obtained.The obtained information in this dissertation may benefit to further understandthe magnetic coupling mechanism that arised from molecular forces and it isalso beneficial to design and synthesize ideal molecular magnets.