Syntheses And Properties Of Coordination Polymers Based On Tripodal Aromatic Multicarboxylate Ligand

Coordination polymers have been applied in many areas,such as fluorescent probes,gas adsorption and separation,magnetic properties,and so on.Under solvothermal method,we have synthesized fifteen novel coordination polymers based on tris?4-carboxylphenyl?phosphine oxide?H₃TPO?and transition/lanthanide metal ions.And they have been characterized by X-ray single crystal diffraction,powder X-ray diffraction?PXRD?,IR and thermogravimetric?TG?analyses.We have investigated the solid-state luminescent behaviour of complexes 1,2,3,12 and 13,and the ability of luminescent sensing small organic molecules and metal ions.The magnetic properties of 6?7?8 and 15 were studied.Gas adsorption experiment for CO₂?H₂?N₂ of 12 has been performed.Structural analyses indicate that complex 1 is a 3D 3,5-c net when HTPO^2-ligands and{Zn₂?COO?₄}SBUs are regarded as 3-c and 5-c nodes respectively.2 is a interpenetrating 2D layer and expanded to 3D supermolecule structure through hydrogen bond interaction.3-5 are isostructural and 3D 3,4-c net.7 is a 6-c hlx net when{Co₂?COO?₂}SBUs are acted as 6-c nodes.8 is a 3D 3,4,4-c topology structure.9 is a 3-fold interpenetrated 3D sheet structure.Complexes 12-15 are also isostructural and 3D 6-c frameworks when{Eu₂?COO?₂}SBUs are acted as 6-c nodes.Complexes 1,2,3,12 and 13 show great fluorescence properties.They present diverse fluorescence intensities in different organic solvent?DMF,DMSO,methanol,acetonitrile,acetone and n-butyl alcohol?.And they show different degrees of quenching effect for various nitrobenzene derivatives?p-nitrophenol,p-nitrotoluene,p-nitroaniline and nitrobenzene?.For different metal ions,the fluorescence intensities are also different and almost completely quenched in Fe³⁺and Hg²⁺aqueous solutions.Compound 12 has good adsorption performance for CO₂,H₂ and N₂ gas and can adsorb selectively CO₂ gas.It is dominant that antiferromagnetic effect of Co?II?ion between the complexes 6,7 and8.As well as,15 displays antiferromagnetic coupling between Dy^IIIII ions.and single-molecule magnets?SMMs?behaviour.According to the Arrhenius law,fitting of the alternating current data obtained energy barrier of 53.5 K,the?₀?pre-exponential factor?value of 3.1×10^-7s with?values less than 0.10,showing a single relaxation process.