Synthesis And Properties Study Of Novel Europium (?) Complexes With Fuorinated ?-Diketones

The?-diketone europium???complex has been recognized for its large Stokes shift,high fluorescence quantum yield,extremely sharp emission bands and long fluorescence lifetime.These complexes have attracted great attention in the fields of chemistry,biology and physics.They can be used in various display devices,organic light emitting diodes?OLEDs?,fluorescent probes and so on,and have great application prospects in materials.In this paper,six europium complexes of pentafluoro-?-diketone,four europium complexes of trifluoromethyl bis-?-diketones and five europium complexes of binuclear trifluoromethyl?-diketones europium complexes have been designed and synthesized,and their properties have been studied systematically.They are divided into the following three chapters:1.Two pentafuorinated??diketone ligands?PFAP and PFMP?were prepared by theClaisencondensationreactionof4-methoxyacetophenoneor4?-dimethylaminoacetophenone with ethyl pentafluoropropionate under the catalysis of sodium ethoxide,which had been employed to synthesize six novel europium???complexes?II-C1^C6?with ancillary ligands 2,2-dipyridine,1,10-phenanthroline and4,7-diphenyl-1,10-phenanthroline.The synthesized europium???complexes were characterized by FT-IR,¹H NMR,UV-Vis,luminescence spectroscopy,elemental analysis and thermogravimetric analysis.Europium???complexes with the?-diketone PFMP exhibited much better photoluminescence properties than complexes with the?-diketone PFAP.Especially,the europium???complex of the?-diketone PFMP with the auxiliary ligand 2,2-dipyridine displayed the longest lifetime value,the highest quantum yield and good CIE color coordinates in these complexes.2.1,1'-?3,4-dimethylthieno[2,3-b]thiophene-2,5-diyl?bis?4,4,4-trifluorobutane-1,3-dione?were prepared by the Claisen condensation reaction of 1,1'-?3,4-dimethyl-thieno[2,3-b]thiop-hene-2,5-diyl?bis?ethan-1-one?and ethyl trifluoroacetate under the catalysis of sodium ethoxide.The new bis-?-diketone ligand had been employed to synthesize four novel europium???complexes?III-C1^C4?with ancillary ligands2,2-dipyridine,1,10-phenanthroline,4,7-diphenyl-1,10-phenanthroline and H₂O.Their spectroscopic behaviors were studied by FT-IR,¹H NMR,UV-vis and photoluminescence spectroscopic techniques.The photoluminescence intensity,fluorescence lifetime and quantum yield of the complexes II-C2,II-C3 and II-C4 are obviously higher than the complex II-C1 with ancillary H₂O.3.Five bipyrimidine bridged dinuclear europium???complexes?IV-C1^C5?with fluorinated?-diketone?such as 4,4,4-trifluoro-1-?4-fluorophenyl?butane-1,3-dio-ne?TFFP?,4,4,4-trifluoro-1-?4-nitro-phenyl?butane-1,3-dione?TFNP?,4,4,4-trifluo-ro-1-?4-methoxyphenyl?butane-1,3-dione?TFMP?,1-?[1,1'-biphenyl]-4-yl?-4,4,4-trifl-uoro-butane-1,3-dione?BPTF?and 4,4,4-trifluoro-1-?pyridin-3-yl?butane-1,3-dione ?TFPD??were synthesized by using 2,2-dipyrimidine?Bpm?as bridging agent.Their spectroscopic behaviors were studied by FT-IR,¹H NMR,UV-vis and photoluminescence spectroscopic techniques.The results showed that the fluorescence lifetime,photoluminescence intensity and fluorescence quantum yield of europium???complex IV-C4 were significantly higher among these bridged dinuclear Eu???complexes.