Zn2MnSbO6 and Zn2FeSbO6: Two New Polar High-Pressure Ordered Corundum-Type Compounds

IF 7.2 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2024-12-03 DOI:10.1021/acs.chemmater.4c02146

Alessia Provino, Thomas J. Emge, David Walker, Corey E. Frank, Suguru Yoshida, Venkatraman Gopalan, Mark Croft, Zheng Deng, Changqing Jin, Pietro Manfrinetti, Martha Greenblatt

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Abstract

Two new compounds, Zn₂FeSbO₆ and Zn₂MnSbO₆, have been synthesized under high-pressure and high-temperature conditions. The synthesis, single-crystal and powder X-ray diffraction, X-ray absorption near-edge spectroscopy (XANES), optical second harmonic generation (SHG), and magnetic and heat capacity measurements were carried out for both compounds and are described. The lattice parameters are a = 5.17754(6) Å and c = 13.80045(16) Å for Zn₂FeSbO₆ and a = 5.1889(10) Å and c = 14.0418(3) Å for Zn₂MnSbO₆. Single-crystal X-ray diffraction analyses indicate that Zn₂FeSbO₆ consists of a cocrystal of superimposed Ni₃TeO₆ (NTO) and ordered ilmenite (OIL) components with a ratio of approximately 2:1 and Zn₂MnSbO₆ contains two nearly identical, but noncrystallographically related, OIL components in a ratio of approximately 6:1. XANES analysis shows Fe³⁺ and Mn³⁺ as formal oxidation states for Fe and Mn cations, respectively, for these A₂BB′O₆ compounds. SHG measurements for Zn₂MnSbO₆ indicate that it is noncentrosymmetric and confirm the polar R3 (no. 146) space group strongly implied by single-crystal reflection data. The magnetic measurements reveal spin-glass behavior with antiferromagnetic (AFM) interactions in both compounds and a frustration factor (f) being significantly larger for Zn₂MnSbO₆ (f ≈ 20) compared to Zn₂FeSbO₆ (f ≈ 7). While Zn₂FeSbO₆ exhibits AFM ordering at a Néel temperature (T_N) of 9 K, Zn₂MnSbO₆ shows magnetic ordering around 4 K. Additionally, the negative Curie–Weiss temperatures for both compounds corroborate the presence of AFM exchange interactions.

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来源期刊

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.