Synthesis, Structure, Photoluminescence And Thermal Properties Of Cu～Ⅰ/Zn～Ⅱ Metal Coordination Polymers Based On Pyrazole

This thesis focuses on the Cu^I or Zn^II d¹⁰ metal complexes based on bipyrazole, and then proposes some new methods and thoughts in the self-assembly of poly-dimensional structures and controlled design of functional coordination compounds through pre-designing the secondary building units as the structural and functional carriers. The thesis is divided into four chapters.In chapter 1, the background of this study, especially the current survey of crystal engineering, and the approach to the designed assembly, and some factors affecting the self-assembly, are introduced. Bipyrazole is selected as bridged ligand, which is based on three points of consideration, the first is the simple coordination fashion of this ligand which contributes to control the structure of metal-organic framework possibly; the second is that this ligand has much advantage to construct poly-dimensional structures; and the last is that some novel frameworks can be constructed by using bipyrazolate ligand.In chapter 2, the successful design and synthesis of Cu^I coordination polymers with pyrazolate and bipyrazolate are described, in which complex 1 was revealed an oligomer and compound 2 a three dimensional framework, presenting the novel topology and eight-fold interpenetration. This investigation demonstrates the tactic of pre-designing the secondary building unit as structural and functional carrier is a very effective method. Furthermore, the details of the synthesis of bipyrazole ligand have been presented.In chapter 3, the aim of this chapter is to study the second ligands' effects in the course of the supramolecular construction. The second ligands include terephthalic acid, isophthalic acid, benzene-1,3,5-tricarboxylic acid, 2,5-pyridine-dicarboxylic acid and 2,6-pyridine- dicarboxylic acid. Under exactly the same reaction conditions except for the second ligand, five Zn^II d¹⁰ metal complexes were obtained. Their structures illustrate that the carboxylic acids affect...