Studies On Complexes Of 4-Acyl Pyrazolone Derivatives

Compounds of acylhydrazone exhibit different coordination modes and their complexes exhibit interesting photophysical properties and magnetic properties. It is important to develop and synthesize new novel lanthanide and transition metal ion complexes using hydrazone of 4-acyl pyrazolones.In the hunt for obtaining superior complexes with novel architectures and fluorescence and amplifying the scope of 4-acyl pyrazolone derivatives, a series of novel 4-acyl pyrazolone derivatives and their lanthanide, transiton metal ions and F-B complexes have been synthesized and characterized on the basis of single crystal X-ray diffractions and some complexes were investigated on the basis of their photophisical properties and magnetic properties. The design strategy of chemosensor was developed by means of supramolecular approach and the relationship between structure and properties were analysized in detail. This thesis is divided into five parts:1. The background of this work is concisely introduced with the emphasis on the current survey of pyrazolone derivatives, design principle of chemosensors.2. Shiff-base synthesized by combination of 4-benzoyl-5-hydroxyl-3-methyl-phenyl pyrazolone and salicylidene hydrazine was chosen as ligand. Its lanthanide (Pr³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Tb³⁺) complexes were synthesized and characterized by single crystal X-ray diffractions. Their fluorescence properties were investigated. Through analysis of the difference in their structure, it was concluded that the peculiar hydrongen bonding in the ligand determined the coordination geometry of the central metal ion, which influence the effective extent of the energy transfer from the ligand to the lanthanide ions. Meanwhile, a binuclear Cu²⁺ complex was synthesized and characterized by single crystal X-ray diffractions. Its magnetic properties were predicted by comparision with the reported similar Cu²⁺ complexes.3. Shiff-base synthesized by combination of 4-benzoyl-5-hydroxyl-3-methyl-phenyl pyrazolone and hydrazine was chosen as ligand. Tb³⁺ and transion metal ions complexes were synthesized and characterized by single crystal X-ray diffractions. Through analysis of the difference in their structure, it was concluded that the peculiar hydrongen bonding in the ligand influenced the coordination geometry of the central metal ion in addition to d electron geometry and ion radius of the central metal ion. Meanwhile, magnetic properties of a binuclear Mn²⁺ complex was investigated and a new oxidation coupling in the symmetric ligand by Mn(OAc)₃ was found.4. A readily available fluorescent sensor [Zn(1-phenyl-3-methyl-5-hydroxy-4-pyrazolylphenyl-ketone benzoylhydrazone)2](Zn-PMPB) with simple and conformationally adaptable receptors for silver cation has been designed by means of supramolecular approach. Zn-PMPB is characterized in detail by various spectroscopic techniques and single-crystal X-ray diffraction. The ¹HNMR, ESI-TOF, UV-Vis suggest that Ag⁺ ions assemblied with Zn-PMPB to yield infinite one dimentional infinite chains structure comprised by [(PMPB₂-Zn)+Ag₂]²⁺ units, The design strategy and remarkable photophysical properties of the sensor reflect the validity of this approach.5. Novel fluorine-boron complexes with donor-acceptor architecture in which pyrazoline-1, 3-diones are chosen as electron donors have been synthesized and well characterized. Correlation of the luminescence properties of the complex L^4c-BF₂ and its crystal structures was discussed. These fluorine-boron complexes show photophysical properties highly dependent on the solvent polarity and aggregation states. The substituents on the pyrazoline were found to have a significant impact on the solid-state luminescent properties. As a result, the evolution of charge transfer modes was observed in solid state.