Brilliant Photoluminescence and Triboluminescence from Ternary Complexes of DyIII and TbIII with 3-Phenyl-4-propanoy1-5-isoxazolonate and a Bidentate Phosphine Oxide Coligand
Brilliant Photoluminescence and Triboluminescence from Ternary Complexes of DyIII and TbIII with 3-Phenyl-4-propanoy1-5-isoxazolonate and a Bidentate Phosphine Oxide Coligand
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DOI：
10.1021/ic400913f
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发表时间：
2013-08-05
影响因子：
4.6
通讯作者：
Reddy, M. L. P.
中科院分区：
文献类型：
--
作者：
Biju, S.;Gopakumar, N.;Reddy, M. L. P.
合成了三个新的稀土杂环β-二酮配合物[Dy（PPI）（3）（EtOH）（2）]（1），[Dy（PPI）（3）（DPEPO）]（2）和[Tb（PPI）（3）（DPEPO）]（3）[其中HPPI = 3-苯基-4-丙酰基-5-异恶唑酮，DPEPO =双（2-二苯基膦基）苯基）醚氧化物]，并对其进行了表征。单晶X-射线衍射分析表明，这些配合物是单核的，并且中心Ln（III）离子与由三个双齿β-二酮配体和乙醇或双齿DPEPO以扭曲的正方形反棱柱几何形状提供的八个氧原子配位。这些配合物具有高的摩尔吸光系数（在285 nm处高达3 × 10（4）M-1 cm（-1）），并且在250 - 350 nm范围内的配体中心带照射时显示出强的可见光和（对于Dy-III）NIR发光。在室温下的发射量子产率和发光寿命为3 +/-0.5%和15 +/-1 μ s的1，12 +/-2%和33 +/-1 μ s的2，和42 +/-6%和795 +/-1 μ s的3。此外，2和3的晶体表现出明亮的摩擦发光，在日光下可见。
Three new lanthanide heterocyclic beta-diketonate complexes [Dy(PPI)(3)(EtOH)(2)] (1), [Dy(PPI)(3)(DPEPO)] (2), and [Tb(PPI)(3)(DPEPO)] (3) [where HPPI = 3-pheny1-4-propanoyl-5-isoxazolone and DPEPO = bis(2(diphenylphosphino)phenyl)ether oxide] have been synthesized and fully characterized. Single-crystal X-ray diffraction analyses reveal that these complexes are mononuclear and that the central Ln(III) ion is coordinated to eight oxygen atoms that are provided by three bidentate beta-diketonate ligands and ethanol or bidentate DPEPO in a distorted square antiprismatic geometry. These complexes have high molar absorption coefficients (up to 3 X 10(4) M-1 cm(-1) at 285 nm) and display strong visible and, for Dy-III, NIR luminescence upon irradiation at the ligand-centered band in the range 250-350 nm. The emission quantum yields and the luminescence lifetimes at room temperature are 3 +/- 0.5% and 15 +/- 1 us for 1, 12 +/- 2% and 33 +/- 1 mu s for 2, and 42 +/- 6% and 795 +/- 1 mu s for 3. Moreover, the crystals of 2 and 3 exhibit brilliant triboluminescence, visible in daylight.