Synthesis and structure of A4V6[Te24+Te6+]O24 (A = K, Rb)—two new quaternary mixed-valent tellurium oxides

Zhu, Tianli; Qin, Jingui; Halasyamani, P. Shiv

doi:10.1039/c1dt10538h

Cited by 8 publications

(4 citation statements)

References 40 publications

(23 reference statements)

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“…We have recently explored the reactions of oxoanions with large bond hyperpolarizabilities with lanthanides to probe structural discontinuities and atypical optical and magnetic properties . Tellurites are particularly rich for a variety of reasons, including variable coordination numbers, the presence of a stereochemically active lone pair of electrons, and the ability to form polymeric anionic networks . The combination of tellurite with sulfate promotes oligomerization, stabilizes low-valent actinides, and leads to large families of lanthanide tellurite sulfates .…”

Section: Introductionmentioning

confidence: 99%

Structure–Property Correlations in the Heterobimetallic 4f/3d Materials Ln₂M(TeO₃)₂(SO₄) (Ln = Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; M = Co or Zn)

Lin

Diefenbach

Silver

et al. 2015

Crystal Growth & Design

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Eighteen new lanthanide transition metal heterobimetallic compounds, Ln 2 Co(TeO 3 ) 2 (SO 4 ) 2 (Ln = Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu) and Ln 2 Zn(TeO 3 ) 2 (SO 4 ) 2 (Ln = Sm, Gd, Dy, Ho, Er, or Yb), have been prepared. They crystallize in triclinic space group P1̅ with two different structural topologies occurring because of a reduction in the Ln 3+ coordination number from eight to seven with the smallest lanthanides, Yb 3+ and Lu 3+ . Magnetic susceptibility studies of compounds with diamagnetic lanthanides and lanthanide-like ions suggest that antiferromagnetic interactions occur between the Co 2+ ions. Similarly, the replacement of Co 2+ with Zn 2+ yields Ln 2 Zn(TeO 3 ) 2 (SO 4 ) 2 (Ln = Gd, Dy, Ho, or Er), and these materials allow for the resolution of the nature of the interactions between lanthanide ions. The data suggest that the short-range Ln 3+ ···Ln 3+ interactions are ferromagnetic. However, a wide range of ferroand antiferromagnetic interactions occur between the Ln 3+ and the Co 2+ cations, with several compounds exhibiting short-range magnetic correlations below 25 K. The results are discussed and contrasted with those recently reported for the related Ln 2 Cu-(TeO 3 ) 2 (SO 4 ) 2 family. ■ INTRODUCTIONHeterometallic coordination compounds, particularly those containing 3d/4f metals, have received an increased level of attention in recent years because of their potential applications in single-molecule magnets (SMMs), 1 ion exchange, 2 gas storage, 3 fluorescence, 4 and optical sensing. 5 The importance of mixed 3d/4f materials is exemplified by their extraordinary magnetic properties as shown by the strongest permanent magnets known, SmCo 5 and Nd 2 Fe 14 B. These latter materials combine the anisotropy of certain lanthanide ions with the itinerant ferromagnetism of transition metals. 6 The introduction of different spin carriers within the same structure type can lead to a vast array of magnetic interactions in heterobimetallic compounds. 7 The diversity of coordination environments exhibited by lanthanides allows a different arrangement between the metal ions, resulting in a variety of magnetic exchange pathways. 8 Orthogonal magnetic orbitals of two different spin carriers can more readily lead to ferromagnetic interactions than in homometallic systems. 9 In addition, a large number of 3d/4f heteronuclear clusters have been reported with magnetic properties that differ greatly from those of homometallic materials. 10 Via investigation of these 3d/4f heterobimetallic systems, important features of molecular magnetism, including the magnetocaloric effect (MCE), 1d quantum tunneling, 1c and slow magnetization relaxation, 11 have been realized.We have recently explored the reactions of oxoanions with large bond hyperpolarizabilities with lanthanides to probe structural discontinuities and atypical optical and magnetic properties. 12 Tellurites are particularly rich for a variety of reasons, including variable coordination numbers, the presence of a stereochemically active lo...

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Section: Introductionmentioning

confidence: 99%

Structure–Property Correlations in the Heterobimetallic 4f/3d Materials Ln₂M(TeO₃)₂(SO₄) (Ln = Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; M = Co or Zn)

Lin

Diefenbach

Silver

et al. 2015

Crystal Growth & Design

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“…Attributable to the weak thermal stability of tellurium compounds, [36][37][38] their synthesis needs to be performed either at relatively low temperature or under sealed conditions. In fact, most reported uranyl tellurium compounds were either from the low-temperature (180-220 °C) hydrothermal method 24,39 or a high-temperature (around 800 °C) flux method 40 which allows the crystal growth at a temperature far below the melting point of the solute.…”

Section: Synthesismentioning

confidence: 99%

Investigation of reactivity and structure formation in a K–Te–U oxo-system under high-temperature/high-pressure conditions

et al. 2016

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The high-temperature/high-pressure treatment of the K-Te-U oxo-family at 1100 °C and 3.5 GPa results in the crystallization of a series of novel uranyl tellurium compounds, K[(UO)(TeO)], K[(UO)TeO], α-K[(UO)TeO] and β-K[(UO)TeO]. In contrast to most of the reported uranyl compounds which are favorable in layered structures, we found that under extreme conditions, the potassium uranyl oxo-tellurium compounds preferably crystallized in three-dimensional (3D) framework structures with complex topologies. Anion topology analysis indicates that the 3D uranyl tellurite anionic framework observed in K[(UO)(TeO)] is attributable to the additional linkages of TeO polyhedra connecting with TeO disphenoids from the neighboring U-Te layers. The structure of K[(UO)TeO] can be described based on [UTeO] clusters, where six TeO polyhedra enclose a hexagonal cavity in which a UO polyhedron is located. The [UTeO] clusters are further linked by TeO square pyramids to form the 3D network. Similar to uranyl tellurates, both α-K[(UO)TeO] and β-K[(UO)TeO] contain TeO octahedra which share a common face to form a dimeric TeO unit. However, in α-K[(UO)TeO], these TeO units connect with UO tetragonal bipyramids to form a 3D structural framework, while in β-K[(UO)TeO], the same TeO dimers are observed to link with UO pentagonal bipyramids, forming 2D layers. Raman measurements were carried out and the vibration bands related to Te-O, Te-O and U-O bonds are discussed.

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“…While lanthanide intermetallic compounds have played keys roles in the development of magneto-structural correlations, oxoanion systems are also extremely well developed . Tellurium-containing oxoanion compounds are particularly rich for a variety of reasons that include variable coordination numbers, the presence of a stereochemically active lone pair of electrons, and the ability for forming polymeric anionic networks for Te(IV) . These compounds, as well as those containing far rarer Te(VI), have been extensively studied by Schleid and co-workers .…”

Section: Introductionmentioning

confidence: 99%

Dimensional and Coordination Number Reductions in a Large Family of Lanthanide Tellurite Sulfates

et al. 2014

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Twenty-two new lanthanide tellurite sulfates with five distinct structures, Ln2(Te2O5)(SO4)2 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb; LnTeSO-1), Ho3(TeO3)2(SO4)2(OH)(H2O) (LnTeSO-2), Ln2TeO3(SO4)2(H2O)2 (Ln = Dy, Ho, Er; LnTeSO-3), Ln2(Te2O5)(SO4)2 (Ln = Er, Tm, Yb, Lu; LnTeSO-4), and Ln2(Te4O10)(SO4) (Ln = Gd, Dy, Ho, Er, Tm, Yb; LnTeSO-5), have been prepared and characterized. The topologies of LnTeSO-1, LnTeSO-2, LnTeSO-3, LnTeSO-4, and LnTeSO-5 are substantially different with respect to the connectivity between Ln polyhedra and the coordination environments of the lanthanide ions. For the first four topologies, the dimensionality changes from layered (LnTeSO-1) to chains (LnTeSO-2) to tetramers (LnTeSO-3) and finally to a monomer (LnTeSO-4). The coordination numbers of lanthanides decrease from nine (LnTeSO-1) to eight (LnTeSO-2 and LnTeSO-3) to seven and six (LnTeSO-4). We attribute the transitions to a decrease in the ionic radii of the 4f ions. Magnetic susceptibility measurements reveal no evidence for long-range magnetic ordering in these materials. However, diverse short-range magnetic correlations were observed within LnTeSO-1.

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Synthesis and structure of A4V6[Te24+Te6+]O24 (A = K, Rb)—two new quaternary mixed-valent tellurium oxides

Cited by 8 publications

References 40 publications

Structure–Property Correlations in the Heterobimetallic 4f/3d Materials Ln₂M(TeO₃)₂(SO₄) (Ln = Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; M = Co or Zn)

Structure–Property Correlations in the Heterobimetallic 4f/3d Materials Ln₂M(TeO₃)₂(SO₄) (Ln = Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; M = Co or Zn)

Investigation of reactivity and structure formation in a K–Te–U oxo-system under high-temperature/high-pressure conditions

Dimensional and Coordination Number Reductions in a Large Family of Lanthanide Tellurite Sulfates

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Synthesis and structure of A4V6[Te24+Te6+]O24 (A = K, Rb)—two new quaternary mixed-valent tellurium oxides

Cited by 8 publications

References 40 publications

Structure–Property Correlations in the Heterobimetallic 4f/3d Materials Ln2M(TeO3)2(SO4) (Ln = Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; M = Co or Zn)

Structure–Property Correlations in the Heterobimetallic 4f/3d Materials Ln2M(TeO3)2(SO4) (Ln = Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; M = Co or Zn)

Investigation of reactivity and structure formation in a K–Te–U oxo-system under high-temperature/high-pressure conditions

Dimensional and Coordination Number Reductions in a Large Family of Lanthanide Tellurite Sulfates

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Product

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Structure–Property Correlations in the Heterobimetallic 4f/3d Materials Ln₂M(TeO₃)₂(SO₄) (Ln = Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; M = Co or Zn)

Structure–Property Correlations in the Heterobimetallic 4f/3d Materials Ln₂M(TeO₃)₂(SO₄) (Ln = Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; M = Co or Zn)