New Noncentrosymmetric Material - [N(CH3)4]ZnCl3: Polar Chains of Aligned ZnCl4 Tetrahedra

Choi, Mun Kee; Kim, Sang‐Hwan; Chang, Hong‐Young; Halasyamani, P. Shiv; Ok, Kang Min

doi:10.1021/ic901064q

Cited by 58 publications

(24 citation statements)

References 65 publications

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“…An organically templated zinc chloride, [N(CH 3 ) 4 ]ZnCl 3 , exhibits a unidimensional crystal structure consisting of corner-shared chains of ZnCl 4 tetrahedra that are separated by [N(CH 3 ) 4 ] + cations (Figure 6). 51 As shown in Figure 6 ). 54 Detailed SHG properties of the NCS materials that are affected by hydrogen-bonding interactions are summarized in Table 2.…”

Section: ■ Effect Of Hydrogen-bonding Interactionsmentioning

confidence: 77%

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 Hydrogen-bonding Interactionsmentioning

confidence: 77%

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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“…It is interesting to note that there are two different structure types in the AMoO 3 (IO 3 ) (A = K, NH 4 , Rb, or Cs) family. KMoO 3 (IO 3 ) with the smallest K + cation in this family exhibits a CS nonpolar space group Pbca , and the others crystallize in polar space group Pna 2 1 , which is mainly due to the rotation of the [MoO 6 ] 6– units to accommodate the increased size of the NH 4 + , Rb + , and Cs + cations. , The hydrogen bond interactions may also be another factor influencing the crystallographic centricities of compounds. , …”

Section: Resultsmentioning

confidence: 99%

Two Polar Molybdenum(VI) Iodates(V) with Large Second-Harmonic Generation Responses

Han

et al. 2019

Chem. Mater.

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Two polar molybdenum(VI) iodates(V), NH4[MoO3(IO3)] (1) and KRb[(MoO3)2(IO3)2] (2), have been prepared by a hydrothermal method. They crystallize in noncentrosymmetric (NCS) space groups Pna21 and Cc, respectively. Structurally, it is interesting that compound 2 has an exclusive one-dimensional [IO3]− chain based on corner-sharing [IO4]3– units in all iodates(V). As for the properties, both compounds exhibit large second-harmonic generation responses of 4.7 × KH2PO4 (KDP) for compound 1 and 8.5 × KDP for compound 2 with phase-matching behavior. These results are in good agreement with the results of the theoretical calculations. In addition, both compounds also possess large birefringences (Δn) of 0.083 at 1064 nm and 0.146 at 1064 nm, respectively. These results indicate that the title compounds will have potential applications as nonlinear optical materials.

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“…[TMFM = (CH 3 ) 3 NCH 2 F] was obtained from the non-ferroelectric (TM)ZnCl 3 [TM = (CH 3 ) 4 N] via H/F substitution, where the fluorinated compound adopts the same mm2 point group as that of the hydrogen-containing analogs (Figure 2A) [43,45]. The introduction of strong electronegative F atom maintains the polar structure and the relatively strong F•••Cl halogen-bonding interaction between [TMFM] + cations and anionic [ZnCl 3 ] − n chains endows the compound with ferroelectricity.…”

Section: Trends In Chemistrymentioning

confidence: 99%

H/F substitution for advanced molecular ferroelectrics

Wang

et al. 2021

Trends in Chemistry

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New Noncentrosymmetric Material - [N(CH₃)₄]ZnCl₃: Polar Chains of Aligned ZnCl₄ Tetrahedra

Cited by 58 publications

References 65 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

Two Polar Molybdenum(VI) Iodates(V) with Large Second-Harmonic Generation Responses

H/F substitution for advanced molecular ferroelectrics

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