Complexation of Europium(III) by Bis(dialkyltriazinyl)bipyridines in 1-Octanol

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• 作者：Michael Steppert ; Ivana C铆sa艡ov谩 ; Thomas Fangh盲nel ; Andreas Geist ; Patric Lindqvist-Reis ; Petra Panak ; Petr 艩t臎pni膷ka ; Sascha Trumm ; Clemens Walther
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：January 2, 2012
• 年：2012
• 卷：51
• 期：1
• 页码：591-600
• 全文大小：495K
• 年卷期：v.51,no.1(January 2, 2012)
• ISSN：1520-510X

文摘

The present work focuses on highly selective ligands for An^III/Ln^III separation: bis(triazinyl)bipyridines (BTBPs). By combining time-resolved laser-induced fluorescence spectroscopy, nanoelectrospray ionization mass spectrometry, vibronic sideband spectroscopy, and X-ray diffraction, we obtain a detailed picture of the structure and stoichiometry of the first coordination sphere of Eu^III-BTBP complexes in an octanolic solution. The main focus is on the 1:2 complexes because extraction studies revealed that those are the species extracted into the organic phase. The investigations on europium(III) complexes of BTBP with different triazin alkylation revealed differences in the formed complexes due to the bulkiness of the ligands. Because of the vibronic sidebands in the fluorescence spectra, we were able to detect whether or not nitrate ligands are coordinated in the first coordination sphere of the Eu-BTBP complexes. In solution, less sterically demanding BTBP offers enough space for additional coordination of anions and/or solvent molecules to form 9-coordinated Eu-BTBP 1:2 complexes, while bulkier ligands tend to form 8-fold-coordinated structures. We also report the first crystal structure of a Ln-BTBP 1:2 complex and that of its 1:1 complex, both of which are 10-coordinated.