A series of oxysulfides RE2M2S3O4(RE = Y, Tm; M = Zr, Hf) featuring a unique MS3O4motif and {[M2S3O4]8−}∞wrinkle layer

Lu, Zhen‐Tao; Yang, Song; Liu, Wenlong; Guo, Sheng‐Ping

doi:10.1039/d1cc00351h

Cited by 11 publications

(3 citation statements)

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“…Besides, the incorporation of diverse structural units can engender a synergistic effect to obtain desired IR NLO properties. Usually, halides have wide band gaps and high LIDTs, and chalcogenides have wide IR transparencies and large NLO responses . Combining these considerations, adducts containing S 8 molecules and another structural unit (such as simple binary halides), which is a rarely investigated NLO application system, aroused our attention.…”

Section: Five Simple Methods To Discover Practical Ir Nlo Candidatesmentioning

confidence: 99%

Rational Design of Novel Promising Infrared Nonlinear Optical Materials: Structural Chemistry and Balanced Performances

Zhou,

Guo

2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Second-order nonlinear optical (NLO) materials are currently a hot topic in modern solid-state chemistry and optics because they can produce coherent light by frequency conversion. Noncentrosymmetric (NCS) structure is not only the prerequisite for NLO materials but also a challengeable issue because materials tend to be centrosymmetric (CS) in terms of thermodynamical stability. Among NLO materials, an excellent infrared (IR) candidate should simultaneously meet several strict key conditions including a large NLO coefficient, high laser-induced damage threshold (LIDT), phase-matchable (PM) behavior, and so on. Achieving a balance between the large NLO effect and high LIDT is difficult, as they have contradictory requirements for chemical bonds. Considering the urgent need of the high-power IR laser market and the drawbacks of the available ones, exploring new highperformance IR NLO crystals is necessary while challenging. In this Account, we first briefly introduce the status and advancement of IR NLO crystals and emphasize the criteria of an excellent candidate. Then, we will introduce five simple methods developed by us to discover practical NLO candidates through understanding of the chemical composition−structure− NLO performance relationship. (1) A rarely investigated system with simple chemical compositions as new-type NLO crystals, namely, adducts containing S 8 molecules, are developed. Combining a chairlike S 8 unit with other units through van der Waals forces has successfully obtained several high-performance NLO adducts. (2) The main trend in exploring new NLO crystals is that the chemical composition is more and more diversified and the structure is more and more complex, and expensive and chemically active alkaline and alkaline earth metals are usually introduced as counter cations. In contrast, the research on systems with simple chemical compositions, simple structures, and low costs has been continuously ignored. The binary M 2 Q 3 (M = Ga, In; Q = S, Se) family with rich acentric modifications has been systematically investigated, and they all exhibit strong SHG effects and high LIDTs. (3) We first proposed the concept of inducing CS structures transformed to NCS ones by partial cation substitution to design novel NLO crystals. Considering the huge number of CS structures in the database compared to the number of NCS structures, it is an attractive method to apply CS structures as the parents to obtain potential NLO materials via partial-substitution-induced symmetry breaking. A series of chalcogenides with high NLO performances have been successfully obtained by us in this way. (4) We investigated the first NLO-active rare earth (RE) chalcophosphates and developed this family systematically, and they demonstrate wonderful comprehensive NLO properties. ( 5) We created a novel mixed-anion system for NLO applications, namely, chalcogenide borates. Usually, mixed-anion compounds can engender a synergistic effect to obtain desired IR NLO properties....

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Section: Five Simple Methods To Discover Practical Ir Nlo Candidatesmentioning

confidence: 99%

Rational Design of Novel Promising Infrared Nonlinear Optical Materials: Structural Chemistry and Balanced Performances

Zhou,

Guo

2024

Acc. Chem. Res.

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“…Widely recognized candidates in this regard are carboxylic acids, carboxylates and inorganic anions. [12][13][14] Compared to ligands with a single coordination site, macrocyclic ligands with multiple pre-organized coordination sites are more suitable for the construction of ZrOCs (HfOCs) due to enhanced coordination through the synergistic coordination of multiple binding groups present in them. 15,16 As a macrocyclic octamer of phenol, p-tert-butylcalix [8]arene (TBC [8]) is considered important, and it is significantly more flexible than calix [4]arene due to ring inversion and can be an excellent ligand for multinuclear MOCs.…”

Section: Introductionmentioning

confidence: 99%

Construction of zirconium/hafnium-oxo clusters based on a new protection-calix[8]arene

Wang,

Hou

2024

Dalton Trans.

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“…In recent years, multiple anionic compounds (MACs) have attracted much attention due to their rich structures and physical properties. − It is commonly believed that the combination of different structural motifs into one structure that can function differently may produce a synergistic effect to realize the desired physical properties. Hitherto, several successful systems have been studied, such as oxysulfides, chalcogenide borates, oxyhalides, and chalcohalides .…”

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Pentanary Oxythiogermanates Ba₃MGe₃O₂S₈ (M = Ca, Zn) Featuring [Ge₃O₂S₈]^8– Trimers and {[MGe₃O₂S₈]^6–}_∞ Chains: Structural Chemistry and Physical Properties

Fan,

Yang,

Yao

et al. 2024

Inorg. Chem.

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Oxychalcogenides are increasingly attracting wide attention because they contain multiple anions that may combine the advantages of oxides and chalcogenides. In this work, two new pentanary oxythiogermanates, Ba 3 MGe 3 O 2 S 8 [M = Ca (1), Zn (2)], were synthesized by a high-temperature solid-state reaction. They crystallize in the orthorhombic space group Pnma, and their structures contain isolated [Ge 3 O 2 S 8 ] 8− units constructed by one [GeO 2 S 2 ] and two [GeOS 3 ] tetrahedra that link with M 2+ ions to build the {[MGe 3 O 2 S 8 ] 6− } ∞ chain, representing a new type of oxythiogermanate. Notably, a [ZnS 5 ] square pyramid exists in 2. Their structural chemistry and relationship with relevant structures are analyzed. 1 and 2 exhibit wide band gaps of 3.93 and 2.63 eV, birefringences of 0.100 and 0.089 at 2100 nm, respectively, and also obvious photocurrent responses. This work may be extended to a family of AE 3 M II M IV 3 O 2 Q 8 (AE = alkali-earth metal; M II = Ca, Zn, Cd, Hg; M IV = Si, Ge, Sn; Q = S, Se), and further systematic survey on them can be performed to enrich the study of multifunctional oxychalcogenides.

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A series of oxysulfides RE₂M₂S₃O₄(RE = Y, Tm; M = Zr, Hf) featuring a unique MS₃O₄motif and {[M₂S₃O₄]⁸⁻}_∞wrinkle layer

Abstract: Inorganic salts with multiple anions recently receive increasing interest in view of their structural diversity and multifunctional properties, and oxysulfides are one type of such salts. Here, three novel oxysulfides...

Cited by 11 publications

References 39 publications

Rational Design of Novel Promising Infrared Nonlinear Optical Materials: Structural Chemistry and Balanced Performances

Rational Design of Novel Promising Infrared Nonlinear Optical Materials: Structural Chemistry and Balanced Performances

Construction of zirconium/hafnium-oxo clusters based on a new protection-calix[8]arene

Pentanary Oxythiogermanates Ba₃MGe₃O₂S₈ (M = Ca, Zn) Featuring [Ge₃O₂S₈]^8– Trimers and {[MGe₃O₂S₈]^6–}_∞ Chains: Structural Chemistry and Physical Properties

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A series of oxysulfides RE2M2S3O4(RE = Y, Tm; M = Zr, Hf) featuring a unique MS3O4motif and {[M2S3O4]8−}∞wrinkle layer

Abstract: Inorganic salts with multiple anions recently receive increasing interest in view of their structural diversity and multifunctional properties, and oxysulfides are one type of such salts. Here, three novel oxysulfides...

Cited by 11 publications

References 39 publications

Rational Design of Novel Promising Infrared Nonlinear Optical Materials: Structural Chemistry and Balanced Performances

Rational Design of Novel Promising Infrared Nonlinear Optical Materials: Structural Chemistry and Balanced Performances

Construction of zirconium/hafnium-oxo clusters based on a new protection-calix[8]arene

Pentanary Oxythiogermanates Ba3MGe3O2S8 (M = Ca, Zn) Featuring [Ge3O2S8]8– Trimers and {[MGe3O2S8]6–}∞ Chains: Structural Chemistry and Physical Properties

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A series of oxysulfides RE₂M₂S₃O₄(RE = Y, Tm; M = Zr, Hf) featuring a unique MS₃O₄motif and {[M₂S₃O₄]⁸⁻}_∞wrinkle layer

Pentanary Oxythiogermanates Ba₃MGe₃O₂S₈ (M = Ca, Zn) Featuring [Ge₃O₂S₈]^8– Trimers and {[MGe₃O₂S₈]^6–}_∞ Chains: Structural Chemistry and Physical Properties