Ionic substitutions in the Cu3TeO6 structure type and magnetic properties of “medium entropy” Cu3/2Mn1/2Co1/2Fe1/2SbO6

Cubic antiferromagnet Cu3TeO6 demonstrates interesting magnetic properties. Aimed at modification of them, we tried multiple ionic substitutions in its structure. However, single-phase materials could only be prepared with large fraction of the Jahn-Teller ions (Cu2+ and Mn3+), although formally iso...

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Bibliographic Details
Published in:Journal of solid state chemistry 2024-12, Vol.340, p.125013, Article 125013
Main Authors: Nalbandyan, V.B., Evstigneeva, M.A., Bazhan, R.V., Vasiliev, A.N., Bulgakov, A.N., Vasilchikova, T.M.
Format: Article
Language:English
Subjects:
Bixbyite
Ionic substitution
Jahn-teller effect
Spin-cluster behavior
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Summary:Cubic antiferromagnet Cu3TeO6 demonstrates interesting magnetic properties. Aimed at modification of them, we tried multiple ionic substitutions in its structure. However, single-phase materials could only be prepared with large fraction of the Jahn-Teller ions (Cu2+ and Mn3+), although formally isostructural bixbyites R2O3 (R4O6) with R = Sc, In, Tl, Sm…Lu exist with no Jahn-Teller ions. Moreover, ions having highest octahedral crystal field stabilization energy (Ni2+ and Cr3+) were found least tolerable. This points to Cu3TeO6 as a separate structure type, distinct from classical bixbyites. We report crystal structure, magnetic and thermodynamic properties of a rare single-phase multicomponent preparation, Cu3/2Mn1/2Co1/2Fe1/2SbO6. The dc magnetic studies show that the formation of the ground spin-cluster state at T = 18 K is preceded by a broad anomaly at ∼122 K. Both specific heat and ac susceptibility data rule out the long-range magnetic ordering, in contrast to closely related Cu2MSbO6 (M = Mn or Fe). One of probable local arrangements of four transition metal cations randomly distributed over the single crystallographic site 24d and spin-cluster glass behavior of magnetization in Cu3/2Mn1/2Co1/2Fe1/2SbO6. [Display omitted] •Cu3TeO6-type solid solutions require large fraction of Cu2+ and/or Mn3+.•Cr3+ and Ni2+ with highest octahedral CFSE are less tolerable than Ga3+, Fe3+ or Co2+.•All of this point to Cu3TeO6 as a separate structure type, distinct from bixbyites.•Competing exchange interactions of multiple magnetic ions lead to spin-cluster state.
ISSN:0022-4596
DOI:10.1016/j.jssc.2024.125013