title: K-edge XANES investigation of octakis(DMSO)lanthanoid(III) complexes in DMSO solution and solid iodides.
abstract: The potential of high energy XANES (X-ray absorption near edge structure) as a tool for the structural analysis of lanthanoid-containing systems has been explored. The K-edge XANES spectra of La(3+), Gd(3+), and Lu(3+) ions both in DMSO solution and solid octakis(DMSO)lanthanoid(III) iodides have been analysed. Although the K-edges of lanthanoids cover the energy range of 38 (La) to 65 (Lu) keV, the large widths of the core hole states do not appreciably reduce the potential structural information of the XANES data. We show that, for lanthanoid compounds, accurate structural parameters are obtained from the analysis of K-edge XANES signals if a deconvolution procedure is carried out. We found that in solid octakis(DMSO)lanthanoid(III) iodides the Ln(3+) ions are coordinated by eight DMSO ligands arranged in a quite symmetric fashion. In DMSO solution the Ln(3+) ions retain a regular eight-coordination structure and the coordination number does not change along the series. In contrast to when in water the second coordination shell has been found to provide a negligible contribution to the XANES spectra of Ln(3+) ions in DMSO solution.
authors: Dipartimento di Chimica, Università di Roma La Sapienza, P.le A. Moro 5, 00185 Roma, Italy. p.dangelo@caspur.it
authors: Paola
authors: P
authors: D'Angelo
authors: Valentina
authors: V
authors: Migliorati
authors: Riccardo
authors: R
authors: Spezia
authors: Simone
authors: S
authors: De Panfilis
authors: Ingmar
authors: I
authors: Persson
authors: Andrea
authors: A
authors: Zitolo
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D004121:Dimethyl Sulfoxide / Q000737:chemistry*; D007454:Iodides / Q000737:chemistry*; D028581:Lanthanoid Series Elements; D008958:Models, Molecular; D012996:Solutions; D056928:X-Ray Absorption Spectroscopy
chemical_list: D056831:Coordination Complexes; D007454:Iodides; D028581:Lanthanoid Series Elements; D012996:Solutions; D004121:Dimethyl Sulfoxide
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