Highly efficient visible light sensitized red emission from europium tris[1-(4-biphenoyl)-3-(2-fluoroyl)propanedione](1,10-phenanthroline) complex grafted on silica nanoparticles
Highly efficient visible light sensitized red emission from europium tris[1-(4-biphenoyl)-3-(2-fluoroyl)propanedione](1,10-phenanthroline) complex grafted on silica nanoparticles
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DOI：
10.1039/c0jm00588f
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发表时间：
2010-01-01
影响因子：
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通讯作者：
Reddy, M. L. P.
中科院分区：
文献类型：
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作者：
Divya, V.;Biju, S.;Reddy, M. L. P.
以1-（4-联苯甲酰基）-3-（2-氟酰基）丙二酮（HBFPD）和1，10-邻菲咯啉为辅助配体，设计、合成、表征了一类新型的可见光敏化Eu ~（3+）天线配合物，并研究了它们的光物理性质。PL测试结果表明，配合物分子中p-共轭的适当扩展使激发带红移到可见光区，因此Eu 3+配合物在蓝光（440 nm）激发下表现出强烈的红光发射，固态量子产率为32 +/-3%，这是迄今为止文献报道的最高值。此外，在本工作中，可见敏化Eu 3+配合物已共价锚定到有序介孔MCM-41通过改性HBFPD配体为第一次尽我们所知。以3-（三乙氧基硅基）丙基异氰酸酯为偶联剂接枝β-二酮为前驱体，制备了介孔纳米材料。通过配体交换反应，将Eu（SiBFPD）（3）（phen）与SiBFPD-Na和1，10-邻菲咯啉（Phen）通过共价键结合在SiO2-Si采用X射线粉末衍射、动态光散射、热重分析、N2吸附-脱附、SEM、TEM、FT-IR、FT-Raman、C-13和Si-29 CPMAS NMR和光致发光光谱等技术对材料进行了表征。与MCM-41共价键合的杂化材料表现出有效的分子内能量转移过程，即“天线效应”，这有利于更强的红色/橙子强度比，更长的寿命，和高的热稳定性比前体配合物。
A novel class of efficient visible light sensitized antenna complexes of Eu3+ based on the use of a highly conjugated b-diketonate, namely, 1-(4-biphenoyl)-3-(2-fluoroyl)propanedione (HBFPD) and 1,10-phenanthroline as an ancillary ligand has been designed, synthesized, characterized and their photophysical properties (PL) investigated. PL measurement results indicated that suitably expanded p-conjugation in the complex molecules makes the excitation band red shift to the visible region and hence the Eu3+ complexes exhibit intense red emission under blue light excitation (440 nm) with a solid-state quantum yield of 32 +/- 3%, which is the highest so far reported in the literature. Further, in the present work, the visible sensitized Eu3+ complex has been covalently anchored to the ordered mesoporous MCM-41 via the modified HBFPD ligand for the first time to the best of our knowledge. beta-Diketonate grafted to the coupling agent 3-(triethoxysilyl)propylisocyanate was used as the precursor for the preparation of mesoporous nanomaterials. MCM-41 consisting of ternary complex Eu(SiBFPD)(3)(phen) covalently bonded to the silica-based network, which was designated as Eu(SiBFPD)(3)(Phen)/MCM-41 (3), was obtained by interacting europium nitrate, SiBFPD-Na and 1,10-phenanthroline into the hybrid material via a ligand-exchange reaction. The designed material was further characterized by powder X-ray diffraction, dynamic light scattering (DLS) technique, thermogravimetric analysis, N-2 adsorption-desorption, SEM, TEM, FT-IR, FT-Raman, C-13 and Si-29 CPMAS NMR and photoluminescence spectroscopic techniques. The hybrid material covalently bonded to MCM-41 exhibits an efficient intramolecular energy transfer process from the silylated bdiketonate to the central Eu3+, namely, the "antenna effect", which favored a stronger red/orange intensity ratio, longer lifetime, and high thermal stability than the precursor complex.