Syntheses,Structures And Properties Of Metal-calix[4,8] Arene Coordination Compounds

Calixarenes,a kind of macrocylic complexes possessing several phenolic group units.The phenolic oxygen atoms and the bridging hetero atoms can bond different metal ions.Thus,their organic backbone can provide a platform for the assembly of several metal centres.This may benefit of generating novel coordination compounds under the auxiliary ligands.In this paper,p-sulfonatothiacalix[4]arene（H4STC₄A）,sulfonylcalix[4]arene（H₄TC₄A-SO₂）and p-tert-butylcalix[8]arene（H₈C₈A）used as the main ligand,under the solvothermal conditions.The obtained Coordination Compounds and structurally determined were characterized by X-ray single crystal diffraction.These compounds were characterized by Infrared spectroscopy（IR）,elemental analysis,thermogravimetric analysis（TG）et al.revealing the relationships between structures and properties for these materials.The main works are as follows:1.The reaction of cobalt acetate with p-sulfonatothiacalix[4]arene（H4STC₄A）and in solvothermal condition.A calixarene-supported {Co₃₂} nanosphere with the diameter being of ca.2-4 nm was obtained.The nanosphere constructed by six CoII4-STC₄ A SBUs bridged by eight {CoIII（μ3-O）3（H₂O）3}3-groups.The fascinating characteristic of the spherical units is given by twenty-four CoII sodalite cage encapsulating eight CoIII cube.The magnetic properties of the coordination compounds indicated antiferromagnetic coupling between the matels.（1）[CoII₂₄CoIII₈（μ3-O）₂4（H₂O）₂4（STC₄A）6]2.A frame-like squares coordination was obtained using H4TC₄ A as the main ligand,a v-shape N-donor ligand 1,3-dis（5H-tertazol-5-yl）benzene（H₂DTB）as the ancillary ligand by solvothermal synthesis and [4+8] condensation.The frame-like squares coordination constructed by four secondary building units（SBUs）of tetranuclear Co4-（TC₄A-SO₂）,bridging with eight H₂ DTB ligands linkers.And they are further stacked extended structure to form many porosity.We carried out the adsorption of hydrogen and nitrogen.（2）[Co₁₆（TC₄A-SO₂）₄（DTB）8（H₂O）₄]3-Two 3d-4f coordination compounds was obtained using H8C8 A as the main ligand and cobalt and rare earth metal ions as the center under the solvothermal conditions.They form two fourteen nuclear of heterometallic coordination compounds,namely Eu6Co₈ and Nd6Co₈.single-crystal X-ray diffraction demonstrated those two structures are featured by some sandwich-like units in which the 3d-4f cluster cores are encapsulated by two calixarene molecules in a tail-to-tail mode.All the C8 A molecules adopt a double cone conformation.（3）[Co₈Eu6（C8A）₂（O）₂（OH）₄（CO₃）₂（HCOO）₂（CH₃COO）₄（DMF）10（H₂O）₄]（4）[Co₈Nd6（C8A）₂（O）₂（OH）₄（CO₃）₂（HCOO）₂（CH₃COO）₄（DMF）10（H₂O）₄]...