A Ferrimagnetic Zintl Phase Pr<sub>4</sub>MnSb<sub>9</sub>: Synthesis, Structure, and Physical Properties

Chen, Xiong; Shen, Jinni; Wu, Li‐Ming; Chen, Ling

doi:10.1021/ic400209x

Cited by 9 publications

(4 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For example, Pr4MnSb9, Ca21Mn4Sb18, Eu10Mn6Sb13, Yb9Zn4Bi9, and Cs13Nb2In6As10 are all new structure types that have no exact main group metalloid analog. 13,14,[22][23][24] Zintl phases containing transition and RE metals have been shown to have unusual and unique magnetic properties, [8][9][10]20 and many Zintl phases have found application as thermoelectric materials. 17,[25][26][27] The first phases defined as Zintl compounds consisted of main group elements and were typically diamagnetic or weakly paramagnetic.…”

Section: Introduction To Zintl Phase Compoundsmentioning

confidence: 99%

The remarkable crystal chemistry of the Ca14AlSb11 structure type, magnetic and thermoelectric properties

Cerretti

Wille

et al. 2019

Journal of Solid State Chemistry

View full text Add to dashboard Cite

Yb14MnSb11 is a member of a remarkable structural family of compounds that are classified according to the concept of Zintl. This structure type, of which the prototype is Ca14AlSb11, provides a flexible framework for tuning structure-property relationships and hence the physical and chemical properties of compounds. Compounds within this family show exceptional high temperature thermoelectric performance at temperatures above 300 K and unique magnetic and transport behavior at temperatures below 300 K. This review provides an overview of the structure variants, the magnetic properties, and the thermoelectric properties. Suggestions for directions of future research are provided. One active research area is to systematically explore more complex compositions such as Ca11Sb10, K4Pb9, Na8Si46, Ca14AlSb11 and KBa2InAs3. 3-7 The other direction is to replace the alkaline earth metals with divalent rare earth elements (Sm, Eu and Yb) along with the introduction of transition metals into structures, typically replacing the less electronegative metalloid in the anionic framework. 8-10 Combinations of these two directions led to compounds such as Yb14MnSb11, Pr4MnSb9, Eu10Mn6Sb13, Yb9Zn4+xBi9 and Cs13Nb2In6As10. 11-16 The complexity of compositions can be combined with a small flexibility in electron counting. For example, Yb14MnSb11 and Yb9Zn4+xBi9 do not strictly follow the Zintl-Klemm concept. Yb14MnSb11 has Mn 2+ instead of a group 13 element such as in Ca14AlSb11 and therefore is electron deficient, 17 and Yb9Zn4+xSb9 has interstitial Zn atoms which can be compositionally varied to achieve specific properties. 18 At the same time, the total number of valence electrons within an identical Zintl phase structure type with different elements may also vary slightly but the variance can be quite small and limited for many structure types that can be described by the Zintl concept. Therefore, with the introduction of transition elements, new electronic properties are possible, but complete transfer of electrons and clear counting of valence electrons remains a criterion for describing transition and rare earth metal containing Zintl phase compounds. Binary Zintl phase compounds which have compositions of simple ratios of elements usually adopt the structures of known oxides or halides, in which anions and cations are isolated in the structure with no covalent bonding. 2, 19 Both isolated anions, polyanions or clusters in Zintl phase compounds can provide complex compositions such as those represented by Ca11Sb10 and K4Pb9. 3, 4 Polyanions or clusters are formed to compensate for lack of enough electrons from the electropositive element to satisfy valence to form a simple one atom anion. Sb forms Sb-Sb single bonds in the Ca11Sb10 structure type resulting in Sb2 4and Sb4 2polyanions in the structure. 3 The Zintl electron counting provides the following charge balanced scenario: 11Ca 2+ + 4Sb 3-+ 2Sb2 4-+ Sb4 2-. Two types of clusters exist in K4Pb9 with the same formal oxidation state: a monocapped square antiprism and a tr...

show abstract

Section: Introduction To Zintl Phase Compoundsmentioning

confidence: 99%

The remarkable crystal chemistry of the Ca14AlSb11 structure type, magnetic and thermoelectric properties

Cerretti

Wille

et al. 2019

Journal of Solid State Chemistry

View full text Add to dashboard Cite

show abstract

“…These compounds are diamagnetic or exhibit weak paramagnetism due to the lack of magnetic ions and precise valence. Later the component elements were expanded to include transition metals and rare earth elements, and compounds such as Yb 14 MnSb 11 , Pr 4 MnSb 9 , Ca 21 Mn 4 Sb 18 , Eu 10 Mn 6 Sb 13 , Yb 9 Zn 4+ x Bi 9 , and Cs 13 Nb 2 In 6 As 10 have been synthesized and studied. − The Mn-containing compounds usually show magnetic order, which opens the study of magnetism in Zintl phases and provides avenues to 3d–4f interactions.…”

Section: Introductionmentioning

confidence: 99%

Tuning Magnetism of [MnSb₄]^9– Cluster in Yb₁₄MnSb₁₁ through Chemical Substitutions on Yb Sites: Appearance and Disappearance of Spin Reorientation

Chen

Cao

et al. 2016

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Single crystals of Yb14-xRExMnSb11 (0 < x < 0.6, RE = Pr, Nd, Sm, and Gd) were synthesized by Sn flux. The compounds are iso-structural with Ca14AlSb11 (I41/acd), and their compositions were determined by wavelength-dispersive spectroscopy. Yb14MnSb11 is described as a partially screened d-metal Kondo system with the isolated [MnSb4](9-) tetrahedral cluster having a d(5) + hole configuration that results in four unpaired electrons measured in the ferromagnetically ordered phase. All of the Yb atoms in Yb14MnSb11 are present as Yb(2+), and the additional RE in Yb14-xRExMnSb11 is trivalent, contributing one additional electron to the structure and altering the magnetic properties. All compounds show ferromagnetic ordering in the range of 39-52 K attributed to the [MnSb4](9-) magnetic moment. Temperature-dependent DC magnetization measurements of Yb14-xPrxMnSb11 (0.44 ≤ x ≤ 0.56) show a sharp downturn right below the ferromagnetic transition temperature. Single-crystal neutron diffraction shows that this downturn is caused by a spin reorientation of the [MnSb4](9-) magnetic moments from the ab-plane to c-axis. The spin reorientation behavior, caused by large anisotropy, is also observed for similar x values of RE = Nd but not for RE = Sm or Gd at any value of x. In Pr-, Nd-, and Sm-substituted crystals, the saturation moments are consistent with ∼4 unpaired electrons attributed to [MnSb4](9-), indicating that local moments of Pr, Nd, and Sm do not contribute to the ferromagnetic order. In the case of RE = Pr, this is confirmed by neutron diffraction. In contrast, the magnetic measurements of RE = Gd show that the moments of Gd ferromagnetically order with the moments of [MnSb4](9-), and reduced screening of moments on Mn(2+) is evident. The sensitive variation of magnetic behavior is attributed to the various RE substitutions resulting in different interactions of the 4f-orbitals with the 3d-orbitals of Mn in the [MnSb4](9-) cluster conducted through 5p-orbitals of Sb.

show abstract

“…Antimonide-based intermetallic-phase compounds receive increasing attention as important materials with interesting physical properties (such as superconductivity and half-metallicity) and diverse structural chemistry of anionic substructures, which endow this family of materials potential applications in magnetic materials, alloy-based anode materials for Li-ion batteries, catalysts, and thermoelectric materials . Intermetallic antimonides are important members of nonclassical Zintl phases, which are intermediates between 2-center-2-electron with delocalized multicenter chemical bonding .…”

Section: Introductionmentioning

confidence: 99%

Soft-Chemical Method for Synthesizing Intermetallic Antimonide Nanocrystals from Ternary Chalcogenide

Jiang

Yuan

et al. 2019

Langmuir

View full text Add to dashboard Cite

The synthesis of intermetallic antimonides usually depends on either the high-temperature alloying technique from highpurity metals or the flux method in highly poisonous Pb-melt. In this paper, we introduced a soft-chemical method to synthesize intermetallic antimonides from ternary chalcogenide precursors under an argon atmosphere below 200 °C. Powder X-ray diffraction and compositional analysis clearly indicate that a new phase of the Ag 3 Sb nanocrystal was synthesized from the Ag 3 SbS 3 precursors. Three types of trialkylphosphines (TAPs) were applied as desulfurization agents, and the transformation mechanism was elucidated. The capability of the desulfurization agent follows the sequence of triphenylphosphine (TPP) > tributylphosphine (TBP) > trioctylphosphine (TOP). Besides, this TAP-driven desulfurization route to synthesize the intermetallic phase could also be possible for AgSbSe 2 and Sb 2 S 3 . Therefore, this paper provides an efficient and mild technique for the fabrication of intermetallic nanocrystals.

show abstract

A Ferrimagnetic Zintl Phase Pr₄MnSb₉: Synthesis, Structure, and Physical Properties

Cited by 9 publications

References 28 publications

The remarkable crystal chemistry of the Ca14AlSb11 structure type, magnetic and thermoelectric properties

The remarkable crystal chemistry of the Ca14AlSb11 structure type, magnetic and thermoelectric properties

Tuning Magnetism of [MnSb₄]^9– Cluster in Yb₁₄MnSb₁₁ through Chemical Substitutions on Yb Sites: Appearance and Disappearance of Spin Reorientation

Soft-Chemical Method for Synthesizing Intermetallic Antimonide Nanocrystals from Ternary Chalcogenide

Contact Info

Product

Resources

About

A Ferrimagnetic Zintl Phase Pr4MnSb9: Synthesis, Structure, and Physical Properties

Cited by 9 publications

References 28 publications

The remarkable crystal chemistry of the Ca14AlSb11 structure type, magnetic and thermoelectric properties

The remarkable crystal chemistry of the Ca14AlSb11 structure type, magnetic and thermoelectric properties

Tuning Magnetism of [MnSb4]9– Cluster in Yb14MnSb11 through Chemical Substitutions on Yb Sites: Appearance and Disappearance of Spin Reorientation

Soft-Chemical Method for Synthesizing Intermetallic Antimonide Nanocrystals from Ternary Chalcogenide

Contact Info

Product

Resources

About

A Ferrimagnetic Zintl Phase Pr₄MnSb₉: Synthesis, Structure, and Physical Properties

Tuning Magnetism of [MnSb₄]^9– Cluster in Yb₁₄MnSb₁₁ through Chemical Substitutions on Yb Sites: Appearance and Disappearance of Spin Reorientation