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Crystallographic an...
Crystallographic and Vibrational Spectroscopic Studies of Octakis(dimethyl sulfoxide)lanthanoid(III) Iodides
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Abbasi, Alireza (författare)
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- Damian Risberg, Emiliana (författare)
- Stockholms universitet,Institutionen för fysikalisk kemi, oorganisk kemi och strukturkemi
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- Eriksson, Lars (författare)
- Stockholms universitet,Avdelningen för oorganisk kemi och strukturkemi
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Mink, Janos (författare)
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Persson, Ingmar (författare)
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- Sandström, Magnus (författare)
- Stockholms universitet,Avdelningen för oorganisk kemi och strukturkemi
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Sidorov, Yurii V. (författare)
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- Skripkin, Mikhail Yu. (författare)
- Stockholms universitet,Avdelningen för oorganisk kemi och strukturkemi
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Ullström, Ann-Sofi (författare)
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(creator_code:org_t)
- 2007-08-24
- 2007
- Engelska.
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 46:19, s. 7731-7741
- Relaterad länk:
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Ämnesord
Stäng
- 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.
Ämnesord
- NATURVETENSKAP -- Kemi -- Oorganisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)
Nyckelord
- Inorganic chemistry
- Oorganisk kemi
Publikations- och innehållstyp
- ref (ämneskategori)
- art (ämneskategori)
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