Synthesis And Properties Of Multifunctional Lanthanide Coordination Polymers And The Hybrid Materials

Lanthanide coordination polymers(CPs)and the related metal-organic-frameworks(MOFs)are a kind of crystalline material.The structures of CPs or MOFs have various possibilities that combine the metal ions and organic ligands.The synthesis of their structures are affected by various factors,such as organic ligands,metal salts,solvent,pH,temperature and cooling rates.As lanthanide coordination polymers containing the specific 4f electronic configuration of lanthanide ion,they can show good performance of optical properties in many fields,especially in the area of luminescence and fluorescence probe.The study and investigation on luminescence,luminescent hybrid materials and fluorescence sensor were performed.The main content of this thesis includes the following:(1)5-methoxy-(4-benzaldehyde)-1,3-benzenedicarboxylic acid(H2L1)ligand was designed and synthesized,and different structures lanthanide coordination polymers were synthesized under hydrothermal condition: Tb2(μ4-L1)2(μ-HL1)(μ-HCOO)(DEF)]n(1)and [Ln(μ4-L1)(L1)(H2O)2]n(Ln=Nd(2),Eu(3)).Their notable feature concerns the presence of free aldehyde groups exposed outside of the metal-organic layer structure,thus allowing the usage of these groups to covalently bind the amine-modified mesoporous MCM-41-NH2 and SBA-15-NH2 materials via the formation of Schiff-base groups.As a result,a new series of luminescent mesoporous hybrid materials based on 2D coordination polymers.The obtained hybrid materials show a number of advantages,as they combine the strength,high thermal stability,and porosity of host matrices with excellent luminescent properties of guest coordination polymers.All the hybrid materials were fully characterized,their luminescent properties were studied in detail.They are also made by coating the UV-LED bulbs with the obtained hybrid materials and the hybrid materials have a promising use in the fabrication of light emitting devices.(2)A series of coordination polymers [Ln(L1)2(Phen)]n(Ln=Eu(16),Tb(17))were synthesized with mixed ligand of H2L1 and phenanthroline(Phen)under hy-drothermal condition.The obtained coordination polymers have the similar structure,which show the two-dimensional structure.The luminescence properties of the two coodination polymers are measured,and also study the abilities of sensing solvent molecules and amines of complex 1 and complex 5.Moreover,the thin-films are prepared by the two sensing materials and applied to sensing the amines vapor.(3)Two series of three-dimensional lanthanide MOFs,[La(L2)(DMF)]n(6)and [Ln4(L2)2(HCOO)(DMF)(OH)2(H2O)2]n(Ln=Sm(7),Eu(8),Gd(9),Tb(10),Dy(11),Er(12),Yb(13))were synthesized with 5-(2’,5’-dicarboxylphenyl)-pyridine-3-carboxylic acid ligand under hydrothermal condition.The crystal structures of complexes show that they are both three-dimensional and have one-dimensional channels.The luminescence properties of the two series coodination polymers were studied,respectively.And as the excellent fluorescence performance of complex 10,it can be applied to sensing solvent molecules,cations and lanthanide cations.