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
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
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DOI：
10.1021/ic1015324
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发表时间：
2010-10-04
影响因子：
4.6
通讯作者：
Cowley, Alan H.
中科院分区：
文献类型：
--
作者：
Raj, D. B. Ambili;Francis, Biju;Cowley, Alan H.
合成了一种新型高效的Eu~(3+)[Eu(CPFHP)_3(DDXPO)]与高氟咔唑取代的对二酮酮配体1-(9H-carbazol-2-yl)-4，4，5，5，5-pentafluoro-3-hydroxypent-2-en-1-one(CPFHP)和4，5-bis(diphenylphosphino)-9，9-dimethylxanthene氧化物(DDXPO)辅助配体负载的新型天线配合物，对其结构进行了表征，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，该配合物是单核的，中心Eu3+离子被8个氧原子包围，其中6个氧原子是由三个双齿β-二酮配体提供的。其余两个氧原子由CHELA：ING氧膦配体提供。配位多面体最好的描述是一个扭曲的正方形反棱镜。Eu(CPFHP)(3)(DDXPO)的光物理性质得益于配体对金属的非辐射失活以及有效的配体到金属的能量转移过程，在氯仿溶液中，配体到金属的能量转移超过66%，量子产率为47%。作为本工作的组成部分，还报道了掺Eu(CPFHP)(3)(DDXPO)的聚甲基丙烯酸甲酯(PMMA)聚合物薄膜的合成、表征和发光性能。与前驱体络合物相比，掺杂薄膜的发光效率显著提高(光致发光量子产率为79-84%)。因此，新型发光PMMA掺杂的Eu(CPFHP)(3)(DDXPO)配合物在聚合物发光二极管和有源聚合物光纤中显示出巨大的应用前景。
A novel efficient antenna complex of Eu3+ [Eu(CPFHP)3(DDXPO)] supported by a highly fluorinated carbazole-substituted P-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 Eu3+ ion is surrounded by eight oxygen atoms, six of which are provided by the three bidentate beta-diketonate ligands. The remaining two oxygen atoms are furnished by the chela:ing 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, characterize:ion, 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.