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X-Ray Absorption Fine Structure Spectroscopic Studies of Octakis(dimethyl sulfoxide)lanthanoid(III) Complexes in Solution and in the Solid Iodides
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
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2007 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 46, no 19, 7742-7748 p.Article in journal (Refereed) Published
Abstract [en]

Octakis(DMSO)lanthanoid(III) iodides (DMSO = dimethylsulfoxide), [Ln(OS(CH3)2)8]I3, 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. L3-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 Å, 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 Å (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 LnIII−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(CH3)2)8]3+ complexes, change only insignificantly from Ln = La to Lu. This indicates that there is no appreciable change in the σ-contribution to the S−O bond, probably due to a corresponding increase in the contribution from the sulfur lone pair to the bonding.

Place, publisher, year, edition, pages
American Chemical Society , 2007. Vol. 46, no 19, 7742-7748 p.
National Category
Inorganic Chemistry
URN: urn:nbn:se:su:diva-24306DOI: 10.1021/ic700659uISI: 000249371500016OAI: diva2:197188
Part of urn:nbn:se:su:diva-6843Available from: 2007-05-15 Created: 2007-05-04 Last updated: 2010-10-25Bibliographically approved
In thesis
1. Structure and bonding of sulfur-containing molecules and complexes
Open this publication in new window or tab >>Structure and bonding of sulfur-containing molecules and complexes
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Synchrotron-based spectroscopic techniques enable investigations of the many important biological and environmental functions of the ubiquitous element sulfur. In this thesis the methods for interpreting sulfur K-edge X-ray absorption near edge structure (XANES) spectra are developed and applied for analyses of functional sulfur groups. The influence of coordination, pH, hydrogen bonding, etc., on the sulfur 1s electronic excitations is evaluated by transition potential density functional theory. Analyses have been performed of reduced sulfur compounds in marine-archaeological wood from historical shipwrecks, including the Vasa, Stockholm, Sweden and the Mary Rose, Portsmouth, U.K.. The accumulation of sulfur as thiols in lignin-rich parts of the wood on the seabed is also a probable pathway in the natural sulfur cycle for how reduced sulfur enters fossil fuels via humic matter in anaerobic marine sediments. Sulfur K-edge XANES spectra for several biochemical model compounds and for coexisting isomeric sulfur species in cysteine and sulfite(IV) aqueous solutions have been analyzed with the aid of theoretical calculations. Cysteine derivatives are important for biochemical detoxification, and mercury(II) cysteine complexes in solution have been structurally characterized by means of Extended X-ray Absorption Fine Structure (EXAFS), Raman and 199Hg NMR spectroscopy. Lanthanoid(III) ions were found to coordinate eight dimethyl sulfoxide oxygen atoms in a distorted square antiprism in the solid state and in solution, by combining crystallography, EXAFS, XANES and vibrational spectroscopy. The mean M-O bond distances for the disordered crystal structures are in good agreement with those from the lattice-independent EXAFS studies. The different sulfur K-edge XANES spectra for the dimethyl sulfoxide ligands in the hexasolvated complexes of the trivalent group 13 metal ions, Tl(III), In(III), Ga(III) and Al(III), were interpreted by theoretical calculations.

Place, publisher, year, edition, pages
Stockholm: Institutionen för fysikalisk kemi, oorganisk kemi och strukturkemi, 2007. 105 p.
Sulfur species, x-ray absorption and vibrational spectroscopy, TP-DFT calculations
National Category
Chemical Sciences
Research subject
Structural Chemistry
urn:nbn:se:su:diva-6843 (URN)978-91-7155-423-9 (ISBN)
Public defence
2007-06-05, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00 (English)
Available from: 2007-05-15 Created: 2007-05-04 Last updated: 2010-01-15Bibliographically approved

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