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}
- Department für Chemie, Institut für Anorganische Chemie, Universität zu Köln, Greinstraße 6, 50939 Köln (Germany)
- II. Physikalisches Institut, Universität zu Köln, Zülpicher Straße 77, 50937 Köln (Germany)
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 mictomagnetic behavior at very low temperatures. Display Omitted.
- OSTI ID:
- 22274121
- Journal Information:
- Journal of Solid State Chemistry, Vol. 206; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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