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??3-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??3-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]...