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基于咔唑的氟化 β-二酮配体和 4,5-双(二苯基膦基)-9,9-二甲基氧杂蒽氧化物共配体支撑的聚(甲基丙烯酸甲酯)掺入铕的高发光配合物。

Highly luminescent poly(methyl methacrylate)-incorporated europium complex supported by a carbazole-based fluorinated β-diketonate ligand and a 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene oxide co-ligand.

机构信息

Chemical Sciences and Technology Division, National Institute for Interdisciplinary Science & Technology (NIIST), CSIR, Thiruvananthapuram-695 019, India.

出版信息

Inorg Chem. 2010 Oct 4;49(19):9055-63. doi: 10.1021/ic1015324.

Abstract

A novel efficient antenna complex of Eu(3+) [Eu(CPFHP)(3)(DDXPO)] supported by a highly fluorinated carbazole-substituted β-diketonate ligand, namely, 1-(9H-carbazol-2-yl)-4,4,5,5,5-pentafluoro-3-hydroxypent-2-en-1-one (CPFHP) and the 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene oxide (DDXPO) ancillary ligand, has been synthesized, structurally characterized, and its photoluminescent behavior examined. The single-crystal X-ray diffraction analysis of Eu(CPFHP)(3)(DDXPO) revealed that this complex is mononuclear, and that the central Eu(3+) ion is surrounded by eight oxygen atoms, six of which are provided by the three bidentate β-diketonate ligands. The remaining two oxygen atoms are furnished by the chelating phosphine oxide ligand. The coordination polyhedron is best described as that of a distorted square antiprism. The photophysical properties of Eu(CPFHP)(3)(DDXPO) benefit from adequate protection of the metal by the ligands with respect to non-radiative deactivation as well as an efficient ligand-to-metal energy transfer process which exceeds 66% in chloroform solution with a quantum yield of 47%. As an integral part of this work, the synthesis, characterization, and luminescent properties of poly(methyl methacrylate) (PMMA) polymer films doped with Eu(CPFHP)(3)(DDXPO) are also reported. The luminescent efficiencies of the doped films (photoluminescence quantum yields 79-84%) are dramatically enhanced in comparison with that of the precursor complex. The new luminescent PMMA-doped Eu(CPFHP)(3)(DDXPO) complex therefore shows considerable promise for polymer light-emitting diode and active polymer optical fiber applications.

摘要

一种新型高效的 Eu(3+) 天线复合物[Eu(CPFHP)(3)(DDXPO)],由高度氟化的咔唑取代的β-二酮配体支持,即 1-(9H-咔唑-2-基)-4,4,5,5,5-五氟-3-羟基戊-2-烯-1-酮(CPFHP)和 4,5-双(二苯基膦基)-9,9-二甲基氧杂蒽氧化物(DDXPO)辅助配体合成、结构表征,并对其光致发光行为进行了研究。Eu(CPFHP)(3)(DDXPO)的单晶 X 射线衍射分析表明,该配合物为单核,中心 Eu(3+)离子被八个氧原子包围,其中六个由三个双齿β-二酮配体提供。其余两个氧原子由螯合膦氧配体提供。配位多面体最好描述为变形的四方反棱柱体。Eu(CPFHP)(3)(DDXPO)的光物理性质得益于配体对金属的充分保护,防止了非辐射失活,以及在氯仿溶液中超过 66%的高效配体到金属的能量转移过程,量子产率为 47%。作为这项工作的一个组成部分,还报道了掺杂 Eu(CPFHP)(3)(DDXPO)的聚甲基丙烯酸甲酯(PMMA)聚合物薄膜的合成、表征和发光性质。与前体配合物相比,掺杂薄膜的发光效率(光致发光量子产率为 79-84%)显著提高。因此,新型发光 PMMA 掺杂 Eu(CPFHP)(3)(DDXPO)配合物在聚合物发光二极管和有源聚合物光纤应用方面具有很大的应用前景。

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