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Title: X-Ray Absorption Fine Structure Spectroscopic Studies of Octakis(DMSO)Lanthanoid(III) Complexes in Solution And in the Solid Iodides

Abstract

Octakis(DMSO)lanthanoid(III) iodides (DMSO = dimethylsulfoxide), [Ln(OS(CH{sub 3}){sub 2}){sub 8}]I{sub 3}, of most lanthanoid(III) ions in the series from La to Lu have been studied in the solid state and in DMSO solution by extended X-ray absorption fine structure (EXAFS) spectroscopy. L{sub 3}-edge and also some K-edge spectra were recorded, which provided mean Ln-O bond distances for the octakis(DMSO)lanthanoid(III) complexes. The agreement with the average of the Ln-O bond distances obtained in a separate study by X-ray crystallography was quite satisfactory. The crystalline octakis(DMSO)lanthanoid(III) iodide salts have a fairly broad distribution of Ln-O bond distances, ca. 0.1 {angstrom}, with a few disordered DMSO ligands. Their EXAFS spectra are in excellent agreement with those obtained for the solvated lanthanoid(III) ions in DMSO solution, both of which show slightly asymmetric distributions of the Ln-O bond distances. Hence, all lanthanoid(III) ions are present as octakis(DMSO)lanthanoid(III) complexes in DMSO solution, with the mean Ln-O distances centered at 2.50 (La), 2.45 (Pr), 2.43 (Nd), 2.41 (Sm), 2.40 (Eu), 2.39 (Gd), 2.37 (Tb), 2.36 (Dy), 2.34 (Ho), 2.33 (Er), 2.31 (Tm), and 2.29 {angstrom} (Lu). This decrease in the Ln-O bond distances is larger than expected from the previously established ionic radii for octa-coordination. This indicates increasingmore » polarization of the Ln{sup III}-O(DMSO) bonds with increasing atomic number. However, the S(1s) electron transition energies in the sulfur K-edge X-ray absorption near-edge structure (XANES) spectra, probing the unoccupied molecular orbitals of lowest energy of the DMSO ligands for the [Ln(OS(CH{sub 3}){sub 2}){sub 8}]{sup 3+} complexes, change only insignificantly from Ln = La to Lu. This indicates that there is no appreciable change in the ?-contribution to the S-O bond, probably due to a corresponding increase in the contribution from the sulfur lone pair to the bonding.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Stanford Linear Accelerator Center (SLAC)
Sponsoring Org.:
USDOE
OSTI Identifier:
953872
Report Number(s):
SLAC-REPRINT-2009-520
Journal ID: ISSN 0020-1669; INOCAJ; TRN: US201004%%609
DOE Contract Number:  
AC02-76SF00515
Resource Type:
Journal Article
Journal Name:
Inorg. Chem. 46:7742,2007
Additional Journal Information:
Journal Volume: 46; Journal Issue: 19; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; ATOMIC NUMBER; AUGMENTATION; BONDING; COMPLEXES; CRYSTALLOGRAPHY; DMSO; ELECTRONS; FINE STRUCTURE; IODIDES; IONS; LIGANDS; POLARIZATION; SALTS; SOLIDS; SOLUTIONS; SPECTRA; SPECTROSCOPY; SULFUR; Other,OTHER, CHEM

Citation Formats

Persson, I., Risberg, E.Damian, D'Angelo, P., Panfilis, S.De, Sandstrom, M., and Abbasi, A. X-Ray Absorption Fine Structure Spectroscopic Studies of Octakis(DMSO)Lanthanoid(III) Complexes in Solution And in the Solid Iodides. United States: N. p., 2009. Web.
Persson, I., Risberg, E.Damian, D'Angelo, P., Panfilis, S.De, Sandstrom, M., & Abbasi, A. X-Ray Absorption Fine Structure Spectroscopic Studies of Octakis(DMSO)Lanthanoid(III) Complexes in Solution And in the Solid Iodides. United States.
Persson, I., Risberg, E.Damian, D'Angelo, P., Panfilis, S.De, Sandstrom, M., and Abbasi, A. Thu . "X-Ray Absorption Fine Structure Spectroscopic Studies of Octakis(DMSO)Lanthanoid(III) Complexes in Solution And in the Solid Iodides". United States.
@article{osti_953872,
title = {X-Ray Absorption Fine Structure Spectroscopic Studies of Octakis(DMSO)Lanthanoid(III) Complexes in Solution And in the Solid Iodides},
author = {Persson, I. and Risberg, E.Damian and D'Angelo, P. and Panfilis, S.De and Sandstrom, M. and Abbasi, A.},
abstractNote = {Octakis(DMSO)lanthanoid(III) iodides (DMSO = dimethylsulfoxide), [Ln(OS(CH{sub 3}){sub 2}){sub 8}]I{sub 3}, of most lanthanoid(III) ions in the series from La to Lu have been studied in the solid state and in DMSO solution by extended X-ray absorption fine structure (EXAFS) spectroscopy. L{sub 3}-edge and also some K-edge spectra were recorded, which provided mean Ln-O bond distances for the octakis(DMSO)lanthanoid(III) complexes. The agreement with the average of the Ln-O bond distances obtained in a separate study by X-ray crystallography was quite satisfactory. The crystalline octakis(DMSO)lanthanoid(III) iodide salts have a fairly broad distribution of Ln-O bond distances, ca. 0.1 {angstrom}, with a few disordered DMSO ligands. Their EXAFS spectra are in excellent agreement with those obtained for the solvated lanthanoid(III) ions in DMSO solution, both of which show slightly asymmetric distributions of the Ln-O bond distances. Hence, all lanthanoid(III) ions are present as octakis(DMSO)lanthanoid(III) complexes in DMSO solution, with the mean Ln-O distances centered at 2.50 (La), 2.45 (Pr), 2.43 (Nd), 2.41 (Sm), 2.40 (Eu), 2.39 (Gd), 2.37 (Tb), 2.36 (Dy), 2.34 (Ho), 2.33 (Er), 2.31 (Tm), and 2.29 {angstrom} (Lu). This decrease in the Ln-O bond distances is larger than expected from the previously established ionic radii for octa-coordination. This indicates increasing polarization of the Ln{sup III}-O(DMSO) bonds with increasing atomic number. However, the S(1s) electron transition energies in the sulfur K-edge X-ray absorption near-edge structure (XANES) spectra, probing the unoccupied molecular orbitals of lowest energy of the DMSO ligands for the [Ln(OS(CH{sub 3}){sub 2}){sub 8}]{sup 3+} complexes, change only insignificantly from Ln = La to Lu. This indicates that there is no appreciable change in the ?-contribution to the S-O bond, probably due to a corresponding increase in the contribution from the sulfur lone pair to the bonding.},
doi = {},
journal = {Inorg. Chem. 46:7742,2007},
issn = {0020-1669},
number = 19,
volume = 46,
place = {United States},
year = {2009},
month = {6}
}