K-edge XANES investigation of octakis(DMSO)lanthanoid(iii) complexes in DMSO solution and solid iodides

Literature Information

Publication Date 2013-04-17
DOI 10.1039/C3CP50842K
Impact Factor 3.676
Authors

Paola D'Angelo, Valentina Migliorati, Riccardo Spezia, Simone De Panfilis, Ingmar Persson, Andrea Zitolo


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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 La3+, Gd3+, and Lu3+ 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 Ln3+ ions are coordinated by eight DMSO ligands arranged in a quite symmetric fashion. In DMSO solution the Ln3+ 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 Ln3+ ions in DMSO solution.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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