LiSc(SeO3)2·xH2O (0 ≤ x ≤ 1): New Selenites Revealing Water Molecule-Driven Extremely High Temperature Single-Crystal-to-Single-Crystal Transformations

Song, Seung Yoon; Ok, Kang Min

doi:10.1021/acs.cgd.6b00519

Cited by 12 publications

(11 citation statements)

References 76 publications

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“…Thus, the Cs + cation should reside in the interlayer space and generate a layered structure of CsIn(SeO 3 ) 2 (Figure c). Similar cation size effects on framework structures have been observed in various stoichiometrically equivalent alkali metal selenites and tellurites. − …”

Section: Effect Of Cation Size On the Centricity And The Framework St...supporting

confidence: 59%

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

2016

Acc. Chem. Res.

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491

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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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Section: Effect Of Cation Size On the Centricity And The Framework St...supporting

confidence: 59%

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

2016

Acc. Chem. Res.

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491

301

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“…LiM(SeO 3 ) 2 (M = Ga, [ 99 ] Sc, [ 100 ] Fe [ 101 ] ) in the NASICON regime presents an intriguing new framework where both the pristine composition LiGa(SeO 3 ) 2 and the Li‐stuffed composition Li 1+1/4 Mg 1/4 Sc 1–1/4 (SeO 3 ) 2 are predicted to have ionic conductivity above 0.1 mS cm −1 (Table 2). The crystal structure of LiGa(SeO 3 ) 2 and Li‐ion probability density from AIMD simulation are shown in Figure 7E,F.…”

Section: Discussionmentioning

confidence: 99%

Lithium Oxide Superionic Conductors Inspired by Garnet and NASICON Structures

Xiao

Jun

Wang

et al. 2021

Advanced Energy Materials

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The key component in lithium solid‐state batteries (SSBs) is the solid electrolyte composed of lithium superionic conductors (SICs). Lithium oxide SICs offer improved electrochemical and chemical stability compared with sulfides, and their recent advancements have largely been achieved using materials in the garnet‐ and NASICON (sodium superionic conductor)‐ structured families. In this work, using the ion‐conduction mechanisms in garnet and NASICON as inspiration, a common pattern of an “activated diffusion network” and three structural features that are beneficial for superionic conduction: a 3D percolation Li diffusion network, short distances between occupied Li sites, and the “homogeneity” of the transport path are identified. A high‐throughput computational screening is performed to search for new lithium oxide SICs that share these features. From this search, seven candidates are proposed exhibiting high room‐temperature ionic conductivity evaluated using ab initio molecular dynamics simulations. Their structural frameworks including spinel, oxy‐argyrodite, sodalite, and LiM(SeO3)2 present new opportunities for enriching the structural families of lithium oxide SICs.

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“…Sc 3+ , Y 3+ , La 3+ , Gd 3+ , and Lu 3+ ) without d-d or f-f electronic transitions have also been pursued as NLO materials that often possess wide optical transparency windows. 38,39 However, all extant rare-earthmetal-based NLO selenites suffer from centrosymmetric (CS) structures or weak SHG responses, [40][41][42] in contrast to some other lone pair cation-containing selenites. [30][31][32][33][34][35][36] Herein, we report the first example of a NCS lutetium selenite crystal, Lu(SeO3)(HSeO3)(H2O)•(H2O) (1), prepared via a hydrothermal synthesis, together with its crystal structure and NLO properties.…”

Section: Introductionmentioning

confidence: 99%

Enhancement of Second-Order Optical Nonlinearity in a Lutetium Selenite by Monodentate Anion Partial Substitution

Lin

et al. 2020

Chem. Mater.

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The systematic modification of the molecular structure of nonlinear optical (NLO)-active materials is a very attractive approach to the improvement of NLO performance. In this study, one lutetium selenite compound Lu(SeO3)(HSeO3)(H2O)•(H2O) (1) was synthesized by hydrothermal means, while a further two lutetium selenites Lu3F(SeO3)4 (2) and Lu(SeO3)(NO3)(H2O) (3) were successfully synthesized by anion partial substitution (APS) of the parent structure 1 under hydrothermal conditions. Specifically, substitution of the [HSeO3] − anions in the noncentrosymmetric 1 by F − or [NO3] − anions with differing denticity leads to the formation of polar 2 and centrosymmetric 3. Our study reveals that the denticity of the secondary functional anions has a significant influence on the coordination environments of the rare-earth metal cation Lu 3+ and consequently the molecular configuration and NLO performance of the resultant multidimensional selenites. In contrast to 1, which displays a weak second-harmonic generation (SHG) response (0.1 × KH2PO4 (KDP)), 2 exhibits a greatly improved NLO performance, including a strong SHG signal (2.5 × KDP, the highest value among rare-earth-metal-based NLO selenites), a wide band gap (3.57 eV) and optical transparency window (0.35−10.3 μm), high thermal stability (~550 °C), and a large laser damage threshold (36 × AgGaS2). These results suggest that 2, as the first example of a fluorinated lutetium selenite, is a strong NLO candidate crystal spanning a region from the near-ultraviolet to the mid-infrared. These APS studies highlight a new feasible approach towards highperformance NLO crystals.

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LiSc(SeO₃)₂·xH₂O (0 ≤ x ≤ 1): New Selenites Revealing Water Molecule-Driven Extremely High Temperature Single-Crystal-to-Single-Crystal Transformations

Cited by 12 publications

References 76 publications

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

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

Lithium Oxide Superionic Conductors Inspired by Garnet and NASICON Structures

Enhancement of Second-Order Optical Nonlinearity in a Lutetium Selenite by Monodentate Anion Partial Substitution

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