Synthesis,Structures And Properties Of Coodnation Polymers Based On Carboxylate Ligands

Coordination polymers have attracted much attention from worldwide researchers,not only because of their interesting structures and intriguing topologies,but also owing to their potential applications in diverse areas,such as gas storage and separation,luminescence,magnetism,catalysis,proton conduction etc.CPs is one kind of metal-organic materials self-assemblyed by metal ions or metal clusters（as nodes）and organic ligands（as linkers）through coordination bonds,which have highly ordered and infinite reticular structures.Choosing proper ligands is of significance for the target CPs’ structures and properties.Carboxylate ligands have been widely used in the construction of CPs for their various coordination modes and strong coordination ability.In this thesis,we focus on the solvothermal synthesis,structures and properties of CPs based on a semi-rigid V-shaped dicarbxoylate and a rigid tricarboxylate ligand.1)Based on a V-shaped H₂hfipbb ligand and some auxiliary linear N-containing ligands,four coordination polymers formulated as[Ni₂（hfipbb）₂（2,2’-bipy）₂（H₂O）₄]（1）,[Ni（4,4’-bipy）（hfipbb）（H₂O）]·0.5DMF（2）,Ni₂（hfipbb）₂（BPE）_1.5（H₂O）（μ₂-H₂O）]·DMF·2H₂O（3）and Zn（hfipbb）（2,2’-bipy）-0.5DMF（4）（H₂hfipbb =4,4’-（hexafluoroisopropylidene）-bis（benzoic acid）;2,2’-bipy = 2,2’-bipyridine;4,4’-bipy ＝4,4’-bipyridine;BPE = 1,2-di（4-pyridyl）ethane;DMF = N,N-dimethylformamide）have been constructed.Compounds 1-4 show diverse structures from OD to 3D network.Moreover compounds 2-4 exhibit hydrophobic properties.The temperature-dependent magnetic susceptibility study shows that compound 3 displays antiferromagnetic coupling between 2K and 300 K.Luminescent measurement shows that compound 4 has photoluminescence at around 385 nm mainly dominated by the ligand-based emission.2)Based on a new tripodal phosphoric carboxylate ligand,tris（p-carboxyl-biphenyl）phosphine oxide（H₃TBPPO）,four novel coordination polymers,namely,Zn₃（TBPPO）₂（5）,Cd₃（TBPPO）₂（6）,Co₃（TBPPO）₂（7）and In（TBPPO）（8）have been synthesized and characterized.Compounds 5,6 and 7 are isostructural,and all of them show flu topological net,while compound 8 possesses a dia network.Compounds 5,6 and 8 all show strong emission bands around 378 nm mainly dominated by the ligand.Remarkably,the luminescent quantum yield of complexes 5,6 and 8 is up to 53.31%,49.02%and 57.31%,respectively.Besides,complex 7 exhibits antiferromagnetism property.