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Title: Change of magnetic and electronic features through subtle substitution in cubic, non-centrosymmetric extended rare-earth metal cluster complexes (TR{sub 3})X{sub 3}

The new compound (IrCe{sub 3})I{sub 3} was synthesized by comproportionation reactions of stoichiometric ratios of CeI{sub 3}, Ce and Ir. Single crystal X-ray diffraction structure determination shows that (IrCe{sub 3})I{sub 3} crystallizes with the cubic variant of the (TR{sub 3})X{sub 3} family (I4{sub 1}32, Z=8, a=12.450(1) Å, V=1930.0(3) Å{sup 3}) and is isostructural with the recently reported (RuLa{sub 3})Br{sub 3}. Octahedral (IrCe{sub 6}) clusters share three common edges forming interpenetrating chains that run along the 4{sub 1} screw axes. Magnetic measurements on pure powder samples of (IrCe{sub 3})I{sub 3} show paramagnetic behavior and, at temperatures below 2 K, a mictomagnetic state. The isostructural (RuLa{sub 3})Br{sub 3} is a Pauli paramagnet suggesting metallic conductivity which is consistent with band structure calculations where the Fermi level is placed below a pseudogap. For (IrCe{sub 3})I{sub 3}, on the contrary, the Fermi level falls in a narrow gap rather than a pseudogap suggesting activated conductivity. - Graphical abstract: The subtle change from (RuLa{sub 3})Br{sub 3} to (IrCe{sub 3})I{sub 3} (IrCe{sub 3})I{sub 3} with the addition of one 5d and one 4f electron changes the magnetic and electronic properties dramatically; (RuLa{sub 3})Br{sub 3} is a Pauli paramagnet, (IrCe{sub 3})I{sub 3} a Langevin paramagnet with mictomagneticmore » behavior at very low temperatures. Display Omitted.« less
Authors:
 [1] ;  [2] ;  [3] ;  [1]
  1. Department für Chemie, Institut für Anorganische Chemie, Universität zu Köln, Greinstraße 6, 50939 Köln (Germany)
  2. II. Physikalisches Institut, Universität zu Köln, Zülpicher Straße 77, 50937 Köln (Germany)
  3. (Germany)
Publication Date:
OSTI Identifier:
22274121
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 206; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; FERMI LEVEL; MONOCRYSTALS; PARAMAGNETISM; POWDERS; RARE EARTHS; X-RAY DIFFRACTION