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Radiochimica Acta

International Journal for chemical aspects of nuclear science and technology

Editor-in-Chief: Qaim, Syed M.

IMPACT FACTOR 2017: 1.202

CiteScore 2017: 1.22

SCImago Journal Rank (SJR) 2017: 0.409
Source Normalized Impact per Paper (SNIP) 2017: 0.869

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Volume 100, Issue 6


Uranyl complexes formed with a para-t-butylcalix[4]arene bearing phosphinoyl pendant arms on the lower rim. Solid and solution studies

F. de M. Ramírez / S. Varbanov
  • 1 Bulgarian Academy of Sciences, Institute of Organic Chemistry with Center of Phot, 1113 Sofia, Bulgarien
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ J.-C. G. Bünzli
  • 2 Ecole polytechnique Fédérale de Lausanne, Institute of Chemical Sciences and Engineering, Lausanne, Schweiz
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  • De Gruyter OnlineGoogle Scholar
/ J. F. Rivas-Silva / M. A. Ocaña-Bribiesca / M. A. Cortés-Jácome / J. A. Toledo-Antonio
Published Online: 2012-01-10 | DOI: https://doi.org/10.1524/ract.2012.1925


The current interest in functionalized calixarenes with phosphorylated pendant arms resides in their coordination ability towards f elements and capability towards actinide/rare earth separation. Uranyl cation forms 1:1 and 1:2 (M:L) complexes with a tetra-phosphinoylated p-tert-butylcalix[4]arene, B4bL4: UO2(NO3)2(B4bL4)n· xH2O (n = 1, x = 2, 1; n = 2, x = 6, 2). Spectroscopic data point to the inner coordination sphere of 1 containing one monodentate nitrate anion, one water molecule and the four phosphinoylated arms bound to UO22+ while in 2, uranyl is only coordinated to calixarene ligands. In both cases the U(VI) ion is 8-coordinate. Uranyl complexes display enhanced metal-centred luminescence due to energy transfer from the calixarene ligands; the luminescence decays are bi-exponential with associated lifetimes in the ranges 220 μs <τs <250 μs and 630 μs <τL < 640 μs, pointing to the presence of two species with differently coordinated calixarene, as substantiated by a XPS study of U(4f5/2,7/2), O(1s) and P(2p) levels on solid state samples. The extraction study of UO22+ cation and trivalent rare-earth (Y, La, Eu) ions from acidic nitrate media by B4bL4 in chloroform shows the uranyl cation being much more extracted than rare earths.

Keywords: Actinides; Lanthanides; Calixarene; Uranyl luminescence; XPS-Extraction

About the article

* Correspondence address: Instituto Nacional de Investigaciones Nucleares, Departamento de Química, Carratera México-Toluca S/N, La Marquesa, Ocoyoacac, C. P. 52750, Mexiko,

Published Online: 2012-01-10

Published in Print: 2012-06-01

Citation Information: Radiochimica Acta International journal for chemical aspects of nuclear science and technology, Volume 100, Issue 6, Pages 359–369, ISSN (Print) 2193-3405 , DOI: https://doi.org/10.1524/ract.2012.1925.

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