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Crystallographic and Vibrational Spectroscopic Studies of Octakis(dimethyl sulfoxide)lanthanoid(III) Iodides
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för fysikalisk kemi, oorganisk kemi och strukturkemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för material- och miljökemi (MMK), Avdelningen för oorganisk kemi och strukturkemi.
Vise andre og tillknytning
2007 (engelsk)Inngår i: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 46, nr 19, s. 7731-7741Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

The octakis(DMSO) (DMSO = dimethylsulfoxide) neodymium(III), samarium(III), gadolinium(III), dysprosium(III), erbium(III), and lutetium(III) iodides crystallize in the monoclinic space group P21/n (No. 14) with Z = 4, while the octakis(DMSO) iodides of the larger lanthanum(III), cerium(III), and praseodymium(III) ions crystallize in the orthorhombic space group Pbca (No. 61), Z = 8. In all [Ln(OS(Me2)8]I3 compounds the lanthanoid(III) ions coordinate eight DMSO oxygen atoms in a distorted square antiprism. Up to three of the DMSO ligands were found to be disordered and were described by two alternative configurations related by a twist around the metal−oxygen (Ln−O) bond. To resolve the atomic positions and achieve reliable Ln−O bond distances, complete semirigid DMSO molecules with restrained geometry and partial occupancy were refined for the alternative sites. This disorder model was also applied on previously collected data for the monoclinic octakis(DMSO)yttrium(III) iodide. At ambient temperature, the eight Ln−O bond distances are distributed over a range of about 0.1 Å. The average value increases from Ln−O 2.30, 2.34, 2.34, 2.36, 2.38, 2.40 to 2.43 Å (Ln = Lu, Er, Y, Dy, Gd, Sm, and Nd) for the monoclinic [Ln(OSMe2)8]I3 structures, and from 2.44, 2.47 to 2.49 Å (Ln = Pr, Ce, and La) for the orthorhombic structures, respectively. The average of the La−O and Nd−O bond distances remained unchanged at 100 K, 2.49 and 2.43 Å, respectively. Despite longer bond distances and larger Ln−O−S angles, the cell volumes are smaller for the orthorhombic structures (Ln = Pr, Ce, and La) than for the monoclinic structure with Ln = Nd, showing a more efficient packing arrangement. Raman and IR absorption spectra for the [Ln(OS(CH3)2)8]I3 (Ln = La, Ce, Pr, Nd, Gd, Tb, Dy, Er, Lu, and Y) compounds, also deuterated for La and Y, have been recorded and analyzed by means of normal coordinate methods. The force constants for the Ln−O and S−O stretching modes in the complexes increase with decreasing Ln−O bond distance and show increasing polarization of the bonds for the smaller and heavier lanthanoid(III) ions.

sted, utgiver, år, opplag, sider
2007. Vol. 46, nr 19, s. 7731-7741
HSV kategori
Identifikatorer
URN: urn:nbn:se:su:diva-24305DOI: 10.1021/ic7006588ISI: 000249371500015OAI: oai:DiVA.org:su-24305DiVA, id: diva2:197187
Merknad
Part of urn:nbn:se:su:diva-6843Tilgjengelig fra: 2007-05-15 Laget: 2007-05-04 Sist oppdatert: 2017-12-13bibliografisk kontrollert
Inngår i avhandling
1. Structure and bonding of sulfur-containing molecules and complexes
Åpne denne publikasjonen i ny fane eller vindu >>Structure and bonding of sulfur-containing molecules and complexes
2007 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
Stockholm: Institutionen för fysikalisk kemi, oorganisk kemi och strukturkemi, 2007. s. 105
Emneord
Sulfur species, x-ray absorption and vibrational spectroscopy, TP-DFT calculations
HSV kategori
Forskningsprogram
strukturkemi
Identifikatorer
urn:nbn:se:su:diva-6843 (URN)978-91-7155-423-9 (ISBN)
Disputas
2007-06-05, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00 (engelsk)
Opponent
Veileder
Tilgjengelig fra: 2007-05-15 Laget: 2007-05-04 Sist oppdatert: 2010-01-15bibliografisk kontrollert

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