Synthesis And Properties Of Supramoleculars And Functional Complexes Baes On The Backbone Of 8-hydroxyquinoline

Owing to their potential applications in organic electroluminescent devices and optical sensor, 8-hydroxyquinoline-based function materials have been concerned about the academic and industrial researchers in recent years. Herein, three multidentate and functionalized organic ligands based on 8-hydroxyquinoline skeletons were synthesized. Based on coordination and supramolecular assembly methods, a variety of 8-hydroxyquinoline-based function materials with novel structures and unique functions were built. The as-synthesized compounds were characterized by a variety of techniques, including single-crystal X-ray diffraction and microanalysis and so on. Additionally, their fluorescence properties were also explored. This thesis includes the following four chapters.In Chapter 1, we summarized the structural features of 8-hydroxyquinoline and recent development of 8-hydroxyquinoline function materials. Additionally, an overview of the thesis topic and progress were also presented.In Chapter 2, one 2-substituted 8-quinolinonate ligand HL₁ containing one pyridyl group and one 8-hydroxyquinoline ligand HL₂ containing imino group were prepared. In the reaction system of the organic ligands?HL₁ and HL₂? and metal ions?Zn2+ and Cd2+?, three organic molecules?4,4'-H₂ BPDB, 2-H₂ ATA, 4,4'-bipyridine? were employed as secondary auxiliary ligands to perform a systematic study on the structural diversities. As a result, five 8-hydroxyquinoline-based coordination polymers were obtained by solvothermal methods. The diverse structures of five complexes indicate that auxiliary ligands play an important role in the assembly of such different frameworks. Moreover, distinct fluorescence properties of the five complexes were observed in the solid state.In Chapter 3, two bis-8-hydroxyquinoline ligands HL₂ and HL₃ were synthesized in three steps. Five porous functional complexs with novel stucrture were prepared by the self-assembly of the Zn??? and Cd??? ions with the two organic ligands, respectively. One mononuclear complex and one binuclear complex was synthesized by reacting HL₃ with Zn???, and Cd??? salt, respectively, which were further assembled into three-dimensional pore structures via C-H??, ??? stacking intermolecular forces. Two kinds of three-dimensional pore structure were assembled by HL₂ and cadmium salt by using different solvent molecules. One pillar coordination cage was prepared from HL₂ and zinc salt. The guest the guest molecules?phenol and para-xylene? can effectively regulate the molecular-packing characteristics of the pillar cage. The crystal phase purity and fluorescence properties of above porous materials were investigated in the solid state.In Chapter 4, Reacting 8-hydroxyquinoline molecule HL₂ with five different acids, five crystalline materials containing different anions were obatained. Their structures were characterized by ¹H NMR, and the reaction processes were investigated by fluorescence titration. The single crystal structure shows that the anions(NO₃^-?Cl^-?SO₄^2-?CF₃COO^- and C₂O₄^2-) can tune the supramolecular structures of five crystalline materials. The crystal material with NO₃^- anion can capsulize some organic functional molecules?phenol, nitrobenzene and ortho methyl nitrobenzene? via its three-dimensional channel. The study of fluorescence properties shows that the anion and the guest molecules can effectively induce the change of the emission wavelength of the crystalline materials.