Preparation, Structure And Fluorescence Properties Of Neodymium Ternary Organic Complexes Based On ?-Diketone

Rare earth organic-inorganic hybrid materials have attracted extensive attention in recent decades because of their special electronic structure,which makes them have some excellent and special properties in optical,electrical and magnetic fields.Especially in the field of fluorescent materials,rare earth functional materials play an important role.Near infrared luminescence of many rare earth ions,including neodymium,has shown special advantages in optical fiber communication,laser system,biofluorescence probe and fluorescence immunoassay.In recent years,many studies in the field of fluorescent materials have focused on rare earth elements.Among them,rare earth organic luminescent complexes are considered as a kind of luminescent materials with wide application prospects.In this paper,four series of ternary?-diketone neodymium complexes were prepared by the method of solution synthesis at room temperature,and their synthesis method,structure,stability and fluorescence properties were studied in detail,and the influence of structure on fluorescence ability was summarized.1.Using?-diketonate as the first ligand and triphenylphosphine oxide as the second ligand,four complexes of?-diketone-triphenylphosphine-neodymium were synthesized by solution method at room temperature.Namely Nd?TTA?₃?TPPO?₂,Nd?BFA?₃?TPPO?₂,Nd??-NTA?₃?TPPO?₂ and Nd?HFA?₃?TPPO?₂.The single crystal structures suitable for X-ray measurement were obtained of Nd?TTA?₃?TPPO?₂,Nd?BFA?₃?TPPO?₂ and Nd?HFA?₃?TPPO?₂.The single crystal analysis shows that the three complexes are typical eight-coordinated structures,and each central neodymium ion and eight oxygen atoms are coordinated to form bonds.The first two crystals form a triangular symmetric structure of the P-1 space group,while the third crystals form a monoclinic symmetric structure of the P21/c space group.The complexes were characterized by infrared spectroscopy,thermogravimetric analysis,elemental analysis and fluorescence spectroscopy.In fluorescence spectra,all complexes exhibit characteristic emission centered on neodymium.2.Four kinds of?-diketone-tri?4-morpholinolino?phosphineoxide-neodymium complexes were synthesized by solution method at room temperature:Nd?C₈H₄F3O2S?3?C12H24N3O4P?2,Nd?C10H6F3O2?3?C12H24N3O4P?2,Nd?C14H8F3O2?3?C12H24N3O₄P?₂ and Nd?C₅H₂F₆O₂?₃(C₁₂H₂₄N₃O₄P)₂,The single crystal structure of Nd?C₅H₂F₆O₂?₃(C₁₂H₂₄N₃O₄P)₂ was obtained.The composition,structure,thermal stability and near infrared fluorescence properties of the complexes were charac-terized and explored by elemental analysis,infrared spectroscopy,thermogravimetric analysis,near infrared fluorescence,X-ray single crystal diffraction and powder diffraction.3.Two neodymium?-diketonates metal-organic complexes,Nd?TTA?₃TPTZ and Nd?BFA?₃TPTZ,have been synthesized by using two?-diketone ligands 4,4,4-tri-fluoro-1-?2-thienyl?-1,3-butanedione and 4,4,4-trifluoro-1-phenyl-1,3-butane-dione,and a macrocyclic conjugate ligand,2,4,6-tri?2-pyridyl?-1,3,5-triazine.The crystal structures of these two complexes were determined by single crystal X-ray diffraction.The X-ray diffraction analysis showed that each neodymium ion in the two complexes formed a Nine-Coordinated structure with six oxygen atoms of HTTA?or HBFA?ligands and three nitrogen atoms of TPTZ ligand by the characteristic of triclinic with P-1 space group both.In the crystal structure of the two complexes,an obvious?-?interaction can be observed between adjacent TPTZ ligand molecules,which play an important role in the formation of three-dimensional structures.The complexes were also characterized by infrared spectroscopy,elemental analysis,thermogravimetric and fluorescence spectra.Fluorescence analysis showed that the two complexes exhibited characteristic neodymium-centered emission due to the significant antenna effect of these ligands.4.Useing?-diketone as the first ligand and trioctylphosphine oxide as the second ligand,four liquid?-diketone-trioctylphosphine oxide-Nd complexes:Nd?TTA?₃?TO PO?₂?Nd?BFA?₃?TOPO?₂?Nd??-NTA?₃?TOPO?₂ and Nd?HFA?₃?TOPO?₂ were synthesized.They were characterized and explored by elemental analysis,infrared spectroscopy,thermogravimetric analysis and near infrared fluorescence.The experimental results show that four series of?-diketone neodymium complexes can react easily at room temperature without heating.The product has good thermal stability,most of which can keep the structure stable at 300^oC.The ligands have good antenna effect,which can effectively transfer energy to the central neodymium ion and generate strong neodymium characteristic fluorescence spectrum under UV-Vis irradiation.This thesis contains 69 Figures,14 Tables,and 187 references.