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Photoluminescence and electrochemiluminescence studies of chosen rare earths systems

Journal of Rare Earths 2008年第2期26卷 192-197页

作者： Stefan Lis Slawomir But krzysztof staninski Monika Jesiolowska Department of Rare Earths Faculty of Chemistry Adam Mickiewicz University Grunwaldzka 6

Eu（Ⅲ） complexes with chosen Keggin polyoxomatalates, POM, containing organic counter cations （tetrabutylarnmonium, tetrabutylphosphonium, triphenylethylphosphonium）, were synthesized, and their photophysical properties were studied. The synthesized complexes had the general formula of XnH5-n[EuSiW11O39], formulated based on the results of elemental and thermogravimetric analysis and FTIR spectroscopy. The photophysical properties of the obtained compounds were investigated using photoluminescence and electrochemiluminescence, ECL, methods in solutions and solids. The most intense luminescence of Eu（Ⅲ） was observed for the complexes with tetrabutylarnmonium cations. After the addition of phenanthroline to the XnH5-n[EuSiW11O39] solutions, a large increase in the Eu（Ⅲ） luminescence intensity and a lengthening of its luminescence lifetime were observed as a result of the formation of ternary complexes. Attempts to apply ECL as a method of light emission by generating species capable of forming excited states in Ln/POMs, i.e., Tb（Ⅲ） and Eu（Ⅲ） in the Na9EuW10O36 and Na9TbW10O36 complexes, were made. The influence of the POM complexes on the ECL was also tested using the Tb/EDDHA （EDDA=ethylenediamine di（o-hydroxyphenylacetic acid）） complex, which is effective in generating ECL.

关键词： Ln(Ⅲ) luminescence electrochemiluminescence polyoxometalates complexes rare earths

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Luminescence study of europium(III) tris(β-diketonato)/phosphonate complexes in chloroform

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Journal of Rare Earths 2008年第2期26卷 185-191页

作者： Stefan Lis Zbigniew Piskula krzysztof staninski Sayaka Tamaki Masayuki Inoue Yuko Hasegawa Department of Rare Earths Faculty of Chemistry Adam Mickiewicz University Grunwaldzka 6 Department of Chemistry Faculty of Science Science University of Tokyo

The extraction of Eu（Ⅲ） with β-diketone, HA, and monodentate or bidentate Lewis bases, B, into chloroform and the luminescence properties of the extracted species were studied. Pivaloyltrifluoroacetone, Hpta, and 2-thenoyltfifluoroacetone, Htta, were used as the β-diketones. The Lewis bases, B, were tetraethyl methylene diphosphonate, POPO, which was bidentate, and diethyl benzylphosphonate, PhPO which was monodentate. Based on the extraction data, the stability constants, log β, of the first complexes between tfis（β-diketonato）Eu（Ⅲ） and the phosphonate, EuA3B, were determined to be 6.0 for the POPO complex and 3.40 for the PhPO complex. The Eu（Ⅲ） luminescence intensity in the EuA3POPO was larger than EuA3 where A was either pta or tta at similar concentrations of Eu（Ⅲ）, while that in Eu（pta）3PhPO was stronger than EuA3; however, in Eu（tta）3PhPO, it was weaker than Eu（tta）3. The POPO functions as a sensitizer, and the PhPO functions as a quencher for the tta chelate and as a sensitizer for the pta chelate. From the lifetime and quantum yield, φ, of the Eu（Ⅲ） luminescence in the complexes as well as the observation of the extractability of Eu（Ⅲ） with the Hpta and the phosphonates and of the luminescence spectra of the complexes, it was confirmed that the extraction of Eu（Ⅲ） was remarkably enhanced with a β-diketonate and a strong Lewis base, and also the ternary complex that was formed as the extracted species, showed luminescence enhancement. This phenomenon may be due the formation of a strong bond between the Eu（Ⅲ） and the strong Lewis base leading to more hydrophobicity in the extracted species and also to more effective energy transfer from the Lewis base to the Eu（Ⅲ）. It was not significant whether the donor atoms were N or O.

关键词： tris(β-diketonato)Eu(Ⅲ) extraction luminescence phosphonate ligands rare earths

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