The Self-Assembly And Properties Of Complex Based On The Cu₄ Precursor Of Thiacalix[4] Arene

Metal-Organic supramolecular chemistry is one of the hot fields in supramolecular chemistry due to its good application prospect in materials,energy,environment,medicine,biology and so on.While one of the key research topics in metal-organic supramolecular chemistry is to assemble metal-organic supermolecule compounds with specific structures and realize their functionalization.Copper-Based supramolecular compounds have been widely taken attention by chemical workers,because of its unique properties in catalysis,gas adsorption and separation,drug release and so on.In this thesis,we use Cu₄-TC4A secondary buiding unit（SBU）which is synthesized by Cu²⁺and H₄TC4A（tert-butylthiacalix[4]arene）as the precursor to assemble differently geometrical clusters of 4f and Cu^Ⅰ-4f clusters as well as copper-based supramolecular compounds through the synergistic effects of different coordination modes and configurations from 4f metal ions,inorganic anions and organic ligands.These results provide us a certain experimental basis and idea for the next researches.The main contents are as follows:（1）The rare earth ions are introduced into the reactive system of H₄TC4A and Cu²⁺to construct two hourglass-shaped cluster of{[Eu₉（TC4A）₂（HCOO）₈（OH）₁₀（H₂O）₈]·（Cl）}（1）and{[Tb₉（TC4A）₂（CH₃COO）₈（OH）₁₀（DMF）₈]·（Cl）}（2）,as well as two metal-crown clusters of{[Cu₄^ⅠEu^Ⅲ（TC4A）₂]·K}（3）and{[Cu₄^ⅠTb^Ⅲ（TC4A）₂]·K}（4）,based on different reaction condition.The presence of large amount of alkali can be beneficial to the reduction of Cu^II into Cu^I and the formation of Cu₄^Ⅰ-Ln clusters.Fluorescence studies show that cluster 1 and 2 have good luminescence properties,the fluorescence intensity of 3 and 4 is very weak.The rare earth ion emission is quenched by Cu⁺because of the energy transfer from f orbital to d orbital.（2）The inorganic anions are introduced into the reactive system of H₄TC4A and Cu²⁺to construct three 3d-metal cage compounds:the ball-shaped cages of{[Cu₂₄（TC4A）₆（OH）₆（CO₃）₈]-（BF₄）₂}（5）based on CO₃^2-anion,[Cu₂₄Na₆（TC4A）₆（OH）₆（PO₄）₈]（6a）based on PO₄^3-and{[Cu₂₄-（TC4A）₆（OH）₆（HPO₄）₈]（BF₄）₂}（6b）based on HPO₄^2-,and the helmet-shaped cage[Cu₂₀（TC4A）₅-（PPOA）₈（OH）₄]（7）based on phenyl phosphonic acid（PPOA）.Structural analysis show that the configuration,charge and coordination mode of inorganic anions have important influence on the structure of the metal-organic supermolecule compounds when the Cu₄-TC4A SBU is assembled with inorganic anions.（3）The organic ligands are introduced into the reactive system of H₄TC4A and Cu²⁺to construct five metal-organic cages:four isomorphically square structures of[Cu₁₆（TC4A）₄（L₁）₈]（8）with isophthalic acid（H₂L₁）,[Cu₁₆（TC4A）₄（HL₂）₈]（9）with 5-hydroxy isophthalic acid（H₃L₂）,[Cu₁₆（TC4A）₄（H₂L₃）₈]（10）with 5-amino isophthalic acid（H₄L₃）and[Cu₁₆（TC4A）₄（L₄）₈]（11）with 5-nitro isophthalic acid（H₂L₄）,a anti-four prismatic cage[Cu₃₂（TC4A）₈（L₅）₈（μ₃-Cl）₈]（12）with 5-tetrazyl isophthalic acid（H₃L₅）,and a double-layered 2D coordination polymer[Cu₄（TC4A）（L₆）（μ₃-Cl）（H₂O）₂]_n（13）with 4,4’,4’’-（nitrilotris（methylene））tribenzoic acid（H₃L₆）.In cages 8,910 and 11,groups hydroxyl,amidogen and nitryl are respectively located in square window and don’t participate in the coordination.We monitor the absorption capacity of compounds 8-11 for dyes in water detected by ultraviolet-visible spectrum.The results indicate that compounds 8-11have the size selectivity for dye molecules,and no charge selectivity;the presence of polar groups can accelerate the adsorption rate of the compounds to the dye.Structural analysis show the configuration,coordination mode,coordination ability,rigidity and flexibility of organic ligands have important influence on the structure of the metal-organic supermolecule compounds when the Cu₄-TC4A SBU is assembled with organic ligands.These results lays the foundation for the synthesis of metal-organic supramolecular compounds with specific configurations.（4）The metal-organic ligands are introduced into the reactive system of H₄TC4A and Cu²⁺to construct an octahedral cage{Cu₂₄（TC4A）₆[Cu₃O（L₇）₃（H₂O）₃]₈（Cl O₄）₈（C₃H₄N₂）₁₂}（14）with trinuclear copper pyrazolate precursors[Cu₃O（HL₇）₃]containing Lewis acid site obtained by the reaction of 4-pyrazolecarboxylic acid（H₂L₇）with Cu（Cl O₄）（CH₃CN）₄,and a 1D zigzag coordinat-ion polymer[Cu₈（TC4A）₂（Cu L₈）（SO₄）₂（H₂O）₆]_n（15）with meso-tetra（4-carboxyphenyl）porphine（H₆L₈）.Porphyrin rings in meso-tetra（4-carboxyphenyl）porphine are complexated with Cu²⁺to form a metal-organic ligand with Lewis acid site.These results show,it’s feasible that the self-assembly of Cu₄-TC4A SBU with metal-organic ligand.These studies lays the foundation for developing the function of metal thiacalix[4]arene self-assembly system.