Energy transfer from Eu(III) and Tb(III) complexes to dyes in their mixed nanostructures. I
Energy transfer from Eu(III) and Tb(III) complexes to dyes in their mixed nanostructures. I
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DOI：
10.1134/s0030400x08020136
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发表时间：
2008-02-01
影响因子：
0.6
通讯作者：
Ermolaev, V. L.
中科院分区：
文献类型：
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作者：
Dudar', S. S.;Sveshnikova, E. B.;Ermolaev, V. L.
在水溶液中观察到了由β-二酮与1，10-菲咯啉的络合物组成的纳米结构的形成，其中涉及多亚甲基、三苯甲烷、恶嗪和黄杂菲系列的染料。结果表明，当Ln(III)离子与染料的络合物浓度在0.5~5mM，染料浓度在5 nm以上时，可以可靠地观察到Ln(III)离子与染料的络合物的纳米结构。研究了配合物Eu(MBTA)(3)phen、Eu(NTA)(3)phen、Eu(PTA)(3)phen、Tb(PTA)(3)phen、Gd(MBTA)(3)phen和Lu(MBTA)(3)phen与染料的纳米结构，其中MBTA为N-甲氧基苯甲酰三氟丙酮，NTA为萘甲酰基三氟丙酮，PTA为蝶酰基三氟丙酮，phen为1，10-邻菲罗啉。结果表明，所形成的纳米结构不仅可以在Ln络合物的纳米结构内含有染料分子，而且可以在其外壳上含有染料分子。证明了当染料浓度在纳摩尔数量级或更高时，Eu络合物与S能级低于Eu(III)的D-5(0)能级的染料形成混合纳米结构，导致Eu(HI)的发光猝灭，引起染料的敏化发光。Eu(III)离子对染料分子的能量转移效率取决于这些分子融入Eu络合物纳米结构的能力。研究了纳米结构的形成对染料发光和吸收光谱形状和位置的影响。比较了Eu，Lu和Gd配合物结构中尼罗蓝的敏化发光强度，结果表明，在纳米结构的配合物中，大部分激发能直接从离子转移到染料分子，而不是通过有机配体的单重态能量转移机制。
The formation of nanostructures that consist of complexes of beta-diketones with 1,10-phenanthroline and involve dyes of the polymethine, triphenylmethane, oxazine, and xanthene series is observed in aqueous solutions. It is found that nanostructures of complexes of Ln(III) ions and dyes are reliably observed at concentrations of Ln complexes from 0.5 to 5 mu M and at dye concentrations above 5 nM. Nanostructures of complexes Eu(MBTA)(3)phen, Eu(NTA)(3)phen, Eu(PTA)(3)phen, Tb(PTA)(3)phen, Gd(MBTA)(3)phen, and Lu(MBTA)(3)phen with dyes are studied, where MBTA is n-methoxybenzoyltrifluoroacetone, NTA is naphthoyltrifluoroacetone, PTA is pivaloyltrifluoroacetone, and phen is 1,10-phenanthroline. It is shown that nanostructures formed can contain dye molecules not only inside a nanostructure of Ln complexes but also on, its outer shell. It is proved that, at a dye concentration in the solution of the order of nanomole or higher, the formation of mixed nanostructures of Eu complexes and dyes whose S, level is below the D-5(0) level of Eu(III) leads to the quenching of the luminescence of Eu(HI) and gives rise to the sensitized luminescence of dyes. The energy transfer efficiency from Eu(III) ions to dye molecules is determined by the ability of these molecules to incorporate into nanostructures of Eu complexes. The effect of the formation of nanostructures on the shape and position of the spectra of luminescence and absorption of dyes is studied. Comparison of the sensitized luminescence intensities of Nile blue in structures of Eu, Lu, and Gd complexes shows that the greater part of the excitation energy of Eu complexes is transferred directly from ions to dye molecules according to the inductive-resonance energy transfer mechanism rather than by means of energy migration over singlet levels of organic ligands in complexes of a nanostructure.