新型β-二酮及其稀土配合物的合成、表征及荧光性能研究

Synthesis, Characterization and Fluorescence Property of a New β-Diketone and Its Rare Earth Complexes

合成了一种新的β-二酮1-(对乙炔基苯基)-1,3-丁二酮(HPB),用元素分析、1HNMR谱及质谱确定了其组成,核磁和红外分析结果表明HPB以烯醇式存在.以HPB分别与Sm(Ⅲ),Eu(Ⅲ),Tb(Ⅲ)和Dy(Ⅲ)反应,合成了四个新的二元稀土配合物,用红外光谱、化学分析、元素分析及热重分析对它们的组成和结构进行了表征.室温下,在紫外光激发下,Sm(Ⅲ),Eu(Ⅲ),Tb(Ⅲ)和Dy(Ⅲ)的配合物表现出中心离子的特征荧光发射.其中Eu(Ⅲ)配合物的发光强度最大,发射谱线很窄,是具有一定应用价值的红色高亮发光材料.通过量子化学计算从理论上对实验结果进行了解释.

A new β-diketone, 1-（p-phenylethynylphenyl）-1,3-butanedione （HPB）, was synthesized and confirmed with elemental analysis, 1H NMR and MS techniques. The result of 1H NMR spectroscopy indicates that the HPB exists as an enol form isomer, which is in good agreement with the result of IR analy-sis. Four new binary rare earth complexes were synthesized by the reaction of HPB with Sm（Ⅲ）, Eu（Ⅲ）, Tb（Ⅲ） and Dy（Ⅲ）, respectively. The compositions of the complexes were characterized by IR spectra, chemical analysis, elemental analysis and thermogravimetric analysis as Sm（PB）3·2H2O, Eu（PB）3·3H2O, Tb（PB）3·2H2O and Dy（PB）3·3H2O. At room temperature, under UV light excitation, the Sm（Ⅲ）, Eu（Ⅲ）, Tb（Ⅲ） and Dy（Ⅲ） complexes exhibit characteristic emission of the central ions. The fluorescence spectra show that the fluorescence emission intensity of Eu（Ⅲ） complex is the strongest. The narrow strongest emission band of Eu（Ⅲ） complex is considered to be a valuable material with bright red fluorescence. The experimental results are interpreted by quantum chemistry calculation.