With 2 - (3 - Amino Pyrazole) - 1, 10 - Neighborhood Coffee Then Lin Ligand Complexes Synthesis And Properties Of The Research

For more than three decades, the study of magnetic properties formolecular-based complexes has been one of advancing disciplines inmagnetic materials. Major advances have been made in the study of magneticproperties for multi-nuclear complexes where the spin-carriers are connectedby bridging ligands and some magneto-structure correlations have beenobtained. However, papers that deal with the magnetic coupling throughintermolecular force are very limited. From the reported papers, intermolecularforce should be one of the key factors that dominate magnetic couplingproperties. But it is far from to understanding thoroughly the relevant magneticcoupling mechanism and no ideal molecule-based ferromagnet has beensynthesized to date. Therefore, it may benefit to design and synthesize newcomplexes and to study magnetic coupling mechanism arising from theintermolecular interaction, such asπ-πstacking and hydrogen bonding, whichinvolves experimental and theoretical calculations. Based on this aspirationeleven novel complexes were designed and synthesized, which include sevenmono-nuclear CuIIcomplexes with 2-（3-amine-pyrazol-1H-yl）-1,10-phenanthroline （phenap） as ligand, namely, two polymorphic complexes 1 and2 （[Cu（phenap）Cl₂]）; complex 3 （[Cu（phenap）（ONO₂）（HOCH₃）]·NO₃）; complex4 （[Cu（phenap）Br₂]）; complex 5 （[Cu（phenap）I₂]）; complex 6 （[Cu（phenap）-NCS]·ClO₄）; complex 7 （[Cu（phenap）（SO₄）（H₂O）]·（H₂O）₂·CH₃OH）. Two multi-nuclear complexes with 2-（1H-imidazl-1-yl）-1,10-phenathroline （phenim） asbridged ligand, namely, complex 8 （[Cu₄（μ-phenim）₄（μ-OCH3）₂（μ-O）₂]·（ClO₄）₄）;complex 9 （{[Cu₂（μ-phenim）₂（μ-OCHO）（OCHO） （H₂O）]·（ClO₄）₂·CH₃CH₂OH}_n）;Two novel CuIIcomplexes with 2-hydroxyl-1,10-phenanthroline （Hophen） asligand, namely, complex 10 （[Cu₂（μ-ophen）₂（Hophen）₂]·（ClO₄）₂）; complex 11（[Cu（Hophen）（C₂O₄）（H₂O）]·H₂O）.For the complexes the infrared spectrum characterization was performed and their crystal structures were determined with X-ray crystallography. Thepowder X-ray diffraction, the elemental analyses, the UV-vis solid reflectancespectra, the thermogravimetric analysis （TGA）, the differential scanningcalorimetry （DSC） measurements and magnetic properties measurements ofthe complex 1 and 2 were performed, which reveals that both the complex 1and 2 possess nearly identical thermal stability and no phase transition hasbeen observed. The variable-temperature magnetic susceptibilitymeasurement for complex 3, 4, 6, 8 and 9 were performed and the fitting onthe obtained magnetic data were made and some magnetic couplingproperties were obtained. In order to understand the correlation between theintermolecular forces and the relevant magnetic coupling properties, thetheoretical calculations of complex 3, 4, 5, 6 and 7 were performed. Thecalculations gave the information involving the spin density, the magneticcoupling sign and the magnetic coupling magnitude of the relevant magneticcoupling pathways. From the above information, the very interestinginformation has been obtained. The obtained information from the elevencomplexes is as follows.1. The intermolecular force can result in magnetic coupling.2. There occurs the spin delocalization on the Cu^Ⅱ3d orbitals to the relevantcoordinated atoms in the studies systems.3. There is spin polarization in the studied systems.4. McConnell I spin polarization mechanism does not explain magneticcoupling sign for all magnetic coupling systems dealing with intermolecularforce magnetic coupling pathways.The obtained information in this dissertation may benefit to understand themagnetic coupling mechanism arisen from intermolecular force and it may alsobenefit to design and synthesize ideal molecule-based ferromagnet, especiallyfor those ferromagnet based on complexes and intermolecular force.