Effect of the Framework Flexibility on the Centricities in Centrosymmetric In2Zn(SeO3)4 and Noncentrosymmetric Ga2Zn(TeO3)4

Lee, Dong Woo; Bak, Dan-bee; Kim, Saet Byeol; Kim, Jiwon; Ok, Kang Min

doi:10.1021/ic300909s

Cited by 49 publications

(24 citation statements)

References 73 publications

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“…13)°, defining a pyramidal shape, which is typical for this type of tellurium-oxygen grouping. 40 However, there are also three long Te-O interactions at 2.941 (4) Å [to O4], compared to the van der Waals separation for these atoms of 3.58 Å. We term this coordination geometry TeO3+3: 41,42 slightly distorted pentagonal face if these O4 … O6 contacts are deemed to be "bonds", in which case, the Te3 species project out of the pentagonal face.…”

Section: Resultsmentioning

confidence: 99%

Lone-pair self-containment in pyritohedron-shaped closed cavities: optimized hydrothermal synthesis, structure, magnetism and lattice thermal conductivity of Co₁₅F₂(TeO₃)₁₄

et al. 2020

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Section: Resultsmentioning

confidence: 99%

Lone-pair self-containment in pyritohedron-shaped closed cavities: optimized hydrothermal synthesis, structure, magnetism and lattice thermal conductivity of Co₁₅F₂(TeO₃)₁₄

et al. 2020

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“…The stoichiometrically similar quaternary mixed metal selenite and tellurite compounds In 2 Zn(SeO 3 ) 4 and Ga 2 Zn(TeO 3 ) 4 , respectively, were synthesized by solid-state reactions. 64 While CS In 2 Zn(SeO 3 ) 4 shows a layered structure composed of distorted InO 6 octahedra, ZnO 6 octahedra, and SeO 3 polyhedra, NCS Ga 2 Zn(TeO 3 ) 4 exhibits a three-dimensional framework with GaO 4 or ZnO 4 tetrahedra and TeO 3 trigonal pyramids (Figure 8). Ga 2 Zn(TeO 3 ) 4 exhibits a moderate SHG efficiency (10 times that of α-SiO 2 ) and is non-phase-matchable (type I).…”

Section: ■ Effect Of Framework Flexibilitymentioning

confidence: 99%

Toward the Rational Design of Novel Noncentrosymmetric Materials: Factors Influencing the Framework Structures

2016

Acc. Chem. Res.

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502

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Solid-state materials with extended structures have revealed many interesting structure-related characteristics. Among many, materials crystallizing in noncentrosymmetric (NCS) space groups have attracted massive attention attributable to a variety of superb functional properties such as ferroelectricity, pyroelectricity, piezoelectricity, and nonlinear optical (NLO) properties. In fact, the characteristics are pivotal to many industrial applications such as laser systems, optical communications, photolithography, energy harvesting, detectors, and memories. Thus, for the past several decades, a great deal of synthetic effort has been vigorously made to realize these technologically important properties by improving the occurrence of macroscopic NCS space groups. A bright approach to increase the incidence of NCS structures was combining local asymmetric units during the initial synthesis process. Although a significant improvement has been achieved in obtaining new NCS materials using this strategy, the majority of solid-state materials still crystallize in centrosymmetric (CS) structures as the locally unsymmetrical units are easily lined up in an antiparallel manner. Therefore, discovering an effective method to control the framework structure and the macroscopic symmetry is an imminent ongoing challenge. In order to more effectively control the overall symmetry of solid-state compounds, it is critical to understand how the backbone and the subsequent centricity are affected during the crystallization. In this Account, several factors influencing the framework structure and centricity of solid-state materials are described in order to more systematically discover novel NCS materials. Recent studies on crystalline solid-state materials suggest three factors affecting the local coordination environment as well as the overall symmetry of the framework structure: (1) size variations of the various template cations, (2) a variable backbone arrangement occurring from the hydrogen-bonding interactions, and (3) the presence of framework flexibility. With regard to the first factor, the impact of size of the various metal cations and coordination numbers on the alignment of other adjacent polyhedra, linkers, and lone pairs determining the framework geometries of mixed metal oxides is analyzed. The second factor considers the regulation of crystallographic centricity determined by the availability of hydrogen-bonding interactions between anionic frameworks containing local asymmetric polyhedra and organic cations. Finally, the third factor explores the framework architecture and the space group symmetry influenced by the flexibility of polyhedra revealing variable coordination numbers. The centricity and framework of new solid-state materials might be controlled by using a variety of synthetically controllable asymmetric units such as organic structure-directing cations and linkers with different sizes and functional groups.

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“…Different types of linkages and different degrees of distortion made for a wide structural flexibility in such tellurites. [27,28] After Fe 2 SO 4 (TeO 3 ) 2 • 3H 2 O [29] was first synthesized and grown in 1971 in the lab, a number of metal tellurite sulfates has been gradually discovered, for instance Cu 7 (OH) 6 (TeO 3 ) 2 (SO 4 ) 2 , [30] M 2 (TeO 3 )(SO 4 ) • H 2 O (M = Co, Mn), [31] [32] An(TeO 3 )(SO 4 ) (An = Pu, Th), Ce 2 (Te 2 O 5 )(SO 4 ) 2 , [33] A 2 Cu 5 (TeO 3 )(SO 4 ) 3 (OH) 4 (A = Na, K), [34] BiCu 2 (TeO 3 )(SO 4 )(OH) 3 , [35] Ln 2 M(TeO 3 ) 2 (SO 4 ) (Ln = Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu, M = Co or Zn). [36] Among the above mentioned tellurite sulfates, the structures of A 2 Cu 5 (TeO 3 )(SO 4 ) 3 (OH) 4 (A = Na, K) [34] contain one dimensional chains, M 2 (TeO 3 )(SO 4 ) • H 2 O (M = Co, Mn), [31] [32] features twodimensional layers and BiCu 2 (TeO 3 )(SO 4 )(OH) 3 [35] shows a 3-D framework.…”

Section: Introductionmentioning

confidence: 99%

“…Similarly, tellurium(IV) can form various oxygen coordination polyhedra, for example, trigonal pyramidal [TeO 3 ] 2− , seesaw [TeO 4 ] 4− , and square pyramidal [TeO 5 ] 6− . Different types of linkages and different degrees of distortion made for a wide structural flexibility in such tellurites [27,28] . After Fe 2 SO 4 (TeO 3 ) 2 ⋅ 3H 2 O [29] was first synthesized and grown in 1971 in the lab, a number of metal tellurite sulfates has been gradually discovered, for instance Cu 7 (OH) 6 (TeO 3 ) 2 (SO 4 ) 2 , [30] M 2 (TeO 3 )(SO 4 ) ⋅ H 2 O (M=Co, Mn), [31] M 3 (TeO 3 )(SO 4 )(OH) 2 ⋅ 2H 2 O (M=Ni, Co), [32] An(TeO 3 )(SO 4 ) (An=Pu, Th), Ce 2 (Te 2 O 5 )(SO 4 ) 2 , [33] A 2 Cu 5 (TeO 3 )(SO 4 ) 3 (OH) 4 (A=Na, K), [34] BiCu 2 (TeO 3 )(SO 4 )(OH) 3 , [35] Ln 2 M(TeO 3 ) 2 (SO 4 ) (Ln=Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu, M=Co or Zn) [36] .…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystal Structures, and Thermal Analyses of Two New Antimony Tellurite Sulfates: [Sb₂(TeO₄)](SO₄) and [Sb₂(TeO₃)₂](SO₄)

Zhang

Zhao

et al. 2021

Zeitschrift anorg allge chemie

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Two new antimony (III) tellurite sulfates [Sb 2 (TeO 4 )](SO 4 ) ( 1) and [Sb 2 (TeO 3 ) 2 ](SO 4 ) (2) were successfully synthesized through a conventional hydrothermal method and their crystal structures were determined by X-ray single crystal analysis.[Sb 2 (TeO 4 )](SO 4 ) crystallizes in the triclinic space group Pī (No. 2) with lattice parameters a = 5.572(2), b = 7.247(2), c = 9.540(3) Å, V = 358.5( 2) Å 3 , and Z = 2, while [Sb 2 (TeO 3 ) 2 ](SO 4 ) crystallizes in the orthorhombic space group Pbca (No. 61) with lattice parameters a = 7.368(2), b = 14.571(3), c = 16.521(3) Å, V = 1773.7(6) Å 3 , and Z = 8. The structure of [Sb 2 (TeO 4 )](SO 4 ) features a three-dimensional framework, composed of [SbO 4 ] trigonal bipyramids and [TeO 4 ] polyhedra to form a cationic 2 1[Sb 2 (TeO 4 )] 2 + corrugated cationic layers along [100], linked by SO 4 2À anions. [Sb 2 (TeO 3 ) 2 ](SO 4 ) forms a three-dimensional framework consisting of two dimensional wrinkled layers of 2 1[Sb 2 (TeO 3 ) 2 ] 2 + that are linked by SO 4 2À anions. The band gaps of 4.16 eV and 3.72 eV for [Sb 2 (TeO 4 )](SO 4 ) and [Sb 2 (TeO 3 ) 2 ](SO 4 ) respectively are estimated from the solid state UV-vis-NIR diffuse reflectance spectra. Thermal analysis indicated that both compounds are thermally stable up to about 500°C. The electrochemical specific capacity of [Sb 2 (TeO 4 )](SO 4 ) was determined to 245 mA h g À 1 on the first cycle in a Li-ion half-cell, the capacity remains at about 106 mA h g À 1 after 500 cycles.

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Effect of the Framework Flexibility on the Centricities in Centrosymmetric In₂Zn(SeO₃)₄ and Noncentrosymmetric Ga₂Zn(TeO₃)₄

Cited by 49 publications

References 73 publications

Lone-pair self-containment in pyritohedron-shaped closed cavities: optimized hydrothermal synthesis, structure, magnetism and lattice thermal conductivity of Co₁₅F₂(TeO₃)₁₄

Lone-pair self-containment in pyritohedron-shaped closed cavities: optimized hydrothermal synthesis, structure, magnetism and lattice thermal conductivity of Co₁₅F₂(TeO₃)₁₄

Toward the Rational Design of Novel Noncentrosymmetric Materials: Factors Influencing the Framework Structures

Synthesis, Crystal Structures, and Thermal Analyses of Two New Antimony Tellurite Sulfates: [Sb₂(TeO₄)](SO₄) and [Sb₂(TeO₃)₂](SO₄)

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Effect of the Framework Flexibility on the Centricities in Centrosymmetric In2Zn(SeO3)4 and Noncentrosymmetric Ga2Zn(TeO3)4

Cited by 49 publications

References 73 publications

Lone-pair self-containment in pyritohedron-shaped closed cavities: optimized hydrothermal synthesis, structure, magnetism and lattice thermal conductivity of Co15F2(TeO3)14

Lone-pair self-containment in pyritohedron-shaped closed cavities: optimized hydrothermal synthesis, structure, magnetism and lattice thermal conductivity of Co15F2(TeO3)14

Toward the Rational Design of Novel Noncentrosymmetric Materials: Factors Influencing the Framework Structures

Synthesis, Crystal Structures, and Thermal Analyses of Two New Antimony Tellurite Sulfates: [Sb2(TeO4)](SO4) and [Sb2(TeO3)2](SO4)

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Effect of the Framework Flexibility on the Centricities in Centrosymmetric In₂Zn(SeO₃)₄ and Noncentrosymmetric Ga₂Zn(TeO₃)₄

Lone-pair self-containment in pyritohedron-shaped closed cavities: optimized hydrothermal synthesis, structure, magnetism and lattice thermal conductivity of Co₁₅F₂(TeO₃)₁₄

Lone-pair self-containment in pyritohedron-shaped closed cavities: optimized hydrothermal synthesis, structure, magnetism and lattice thermal conductivity of Co₁₅F₂(TeO₃)₁₄

Synthesis, Crystal Structures, and Thermal Analyses of Two New Antimony Tellurite Sulfates: [Sb₂(TeO₄)](SO₄) and [Sb₂(TeO₃)₂](SO₄)