Lone-Pair Self-Containment in Tellurite Tubes:  Hydrothermal Syntheses and Structures of BaTe3O7 and BaTe4O9

Johnston, Magnus G.; Harrison, William T. A.

doi:10.1021/ja017648b

Cited by 57 publications

(35 citation statements)

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“…The new mixed-metal selenites Ba 2 Mn 3 (SeO 3 ) 6 and PbFe 2 (SeO 3 ) 4 have been hydrothermally prepared as single crystals and characterized. To the best of our knowledge, they are the first well-characterized binary M/M 0 /selenites to contain these cation combinations.…”

Section: Discussionmentioning

confidence: 99%

“…The occurrence of lone-pair channels of reasonable size and redox-active Mn II /Mn III metal centers in Ba 2 Mn 3 (SeO 3 ) 6 suggests the possibility of redox intercalation in which a process schematically represented by Ba 2 Mn II Mn 2 III (SeO 3 ) 6 +Li-Li x Ba 2 Mn II 1+x Mn III 2Àx (SeO 3 ) 6 (0pxp2) could occur and we are now investigating this possibility further. 4 showing the network of FeO 6 octahedra and SeO 3 E pseudotetrahedra [the dummy atom E (unshaded circle), placed 1.0 Å from Se represents the lone pair of electrons] encapsulating channels at y=0, z=0 and equivalent locations occupied by the lead cations (shaded circles) and empty lone-pair channels at y ¼ 1 2 ; z ¼ 1 2 and equivalent locations.…”

Section: Discussionmentioning

confidence: 99%

“…In this paper, we report the hydrothermal syntheses, single-crystal structures, and some properties of Ba 2 Mn II Mn 2 III (SeO 3 ) 6 and PbFe 2 (SeO 3 ) 4 . These related phases demonstrate a self-containment effect [4] in which the Se IV lone pairs of electrons are directed into otherwise empty, infinite, one-dimensional 8-ring channels of significant size.…”

Section: Introductionmentioning

confidence: 99%

“…These related phases demonstrate a self-containment effect [4] in which the Se IV lone pairs of electrons are directed into otherwise empty, infinite, one-dimensional 8-ring channels of significant size. A similar effect has recently been demonstrated for the phase Tb 2 O(SeO 3 ) 2 , in which the selenite moieties arrange themselves so that their lone pairs occupy channels in a manner that reflects the4 symmetry of other parts of the structure [5].…”

Section: Introductionmentioning

confidence: 99%

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Two new octahedral/pyramidal frameworks containing both cation channels and lone-pair channels: syntheses and structures of Ba2MnIIMn2III(SeO3)6 and PbFe2(SeO3)4

Johnston

Harrison

2004

Journal of Solid State Chemistry

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Two new octahedral/pyramidal frameworks containing both cation channels and lone-pair channels: syntheses and structures of Ba2MnIIMn2III(SeO3)6 and PbFe2(SeO3)4

Johnston

Harrison

2004

Journal of Solid State Chemistry

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“…While there are a few reports on the hydrothermal syntheses of complex tellurium(IV) oxides (BaTe3O7, 9) Mn2Te3O8, 10) and Cs2Mo3TeO12 11) ), only two oxides (CaTe3O8 12) and Rb4Te8O23 13) ) containing tellurium(VI) have been prepared by hydrothermal techniques. Both of the compounds were mixed-valent and prepared by the reactions with H6Te VI O6 as the source of tellurium.…”

Section: )-8)mentioning

confidence: 99%

Hydrothermal synthesis of Cd3TeO6 oxide powders

Tezuka

Kawakami

Shan

et al. 2008

J. Ceram. Soc. Japan

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Hydrothermal preparation of a transparent wide-gap conductor Cd3TeO6 from CdO, TeO2, H2O2, and alkali hydroxide was explored. The reaction without alkali hydroxide yielded only a small amount of Cd3TeO6, and NaOH gave a better yield than LiOH and KOH. The reactions without H2O2 did not form Cd3TeO6 at all. This observation indicated that H2O2 oxidized tellurium (IV) to the oxidation state VI in this system. The reactions at 240°C, the highest temperature available in this study, gave a better yield of Cd3TeO6 than the reactions at lower temperatures. After these optimizations, Cd3TeO6 was obtained as the dominant product.

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Unusual Uranyl Tellurites Containing [Te2O6]4 Ions and Three-Dimensional Networks

Almond¹,

McKee²,

Albrecht‐Schmitt³

2002

Angew. Chem. Int. Ed.

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Solid-state chemistry of the actinides is the subject of significant investigation because of its relevance to nuclear waste disposal and power generation, [1] mineralogy, [2] and catalysis. [3] One system that is poorly understood is that of the uranyl tellurites, which are currently known only from three minerals, UO 2 (Te 3 O 7 ), [4] PbUO 2 (TeO 3 ) 2 , [5] and UO 2 (TeO 3 ), [6] and the synthetic phase Pb 2 UO 2 (TeO 3 ) 3 . [7] In spite of their low representation, these compounds differ substantially in their dimensionality, [2] the coordination environments of the U VI center, and in the Te IV oxoanions present.The ubiquitous presence of a stereochemically active lone pair of electrons on the Te IV centers certainly plays a substantial role in the crystalline architecture of this family of compounds. However, the general tendency is for oxoanions containing nonbonding electrons to either not affect the overall dimensionality of U VI compounds, or to reduce it from two-dimensional to one-dimensional, as demonstrated by uranyl iodates [8, 9] and selenites. [10] In uranyl tellurites this trend is not observed. The ability of Te IV to bind four or five O atoms in its inner sphere, as found in the ternary phases, BaTe 3 O 7 , [11] BaTe 4 O 9 , [11] TeSeO 4 , [12] UO 2 (TeO 3 ), [6] and UO 2 (-Te 3 O 7 ) [4] does not offer a satisfying explanation for the atypical behavior of uranyl tellurites because Pb 2 UO 2 (TeO 3 ) 3 contains only TeO 3 2À ions, and yet it still adopts a threedimensional architecture. [7] To address the unusual bonding in the uranyl tellurite system we are systematically preparing a series of compounds by hydrothermal methods that differ primarily in their countercations. For example, the reaction of TlCl with UO 2 (C 2 H 3 O 2 ) 2 ¥2 H 2 O and Na 2 TeO 3 at 180 8C in aqueous media for three days produces Tl 2 [UO 2 (TeO 3 ) 2 ] (1), whereas, in the absence of TlCl, Na 8 [(UO 2 ) 6 (TeO 3 ) 10 ] (2) is isolated instead.The simplicity of the formula of 1 is quite misleading because its structure is far from predictable. The uranyl tellurite architecture in this compound is constructed from uranyl moieties that are bound by five O atoms to create UO 7 pentagonal bipyramids. These polyhedra edge-share to form dimers. The dimers are joined by bridging TeO 3 2À ions to yield one-dimensional chains. The chains are in turn linked by [Te 2 O 6 ] 4À ions that are bischelating/bridging, producing twodimensional 2 1 [UO 2 (TeO 3 ) 2 ] 2À sheets that are separated by Tl þ ions. Part of a 2 1 [UO 2 (TeO 3 ) 2 ] 2À sheet is illustrated in Figure 1. Bond valence sum calculations are consistent with U VI and COMMUNICATIONS 3426

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Lone-Pair Self-Containment in Tellurite Tubes: Hydrothermal Syntheses and Structures of BaTe₃O₇ and BaTe₄O₉

Cited by 57 publications

References 8 publications

Two new octahedral/pyramidal frameworks containing both cation channels and lone-pair channels: syntheses and structures of Ba2MnIIMn2III(SeO3)6 and PbFe2(SeO3)4

Two new octahedral/pyramidal frameworks containing both cation channels and lone-pair channels: syntheses and structures of Ba2MnIIMn2III(SeO3)6 and PbFe2(SeO3)4

Hydrothermal synthesis of Cd3TeO6 oxide powders

Unusual Uranyl Tellurites Containing [Te2O6]4 Ions and Three-Dimensional Networks

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