Li6M(SeO3)4 (M = Co, Ni, and Cd) and Li2Zn(SeO3)2: Selenites with Late Transition-Metal Cations

Jo, Hongil; Lee, Suheon; Choi, K.-Y.; Ok, Kang Min

doi:10.1021/acs.inorgchem.8b00305

Cited by 27 publications

(17 citation statements)

References 68 publications

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“…Bi (1) and Bi(2) are sevencoordinated with five Op lus two Fa toms, and four Op lus three Fa toms, respectively.T he bond lengths of BiÀOa nd BiÀ Ff all in the range of 2.217(9)-2.547(9) and 2.417(7)-2.663(8) ,r espectively.T he Ti(1) cation is coordinated by four oxygen and two fluorine atoms in an octahedral environment with the TiÀO/F bond lengthsr anging from 1.911(7) to 1.973(8) .T he Se IV cations are connected with three oxygen atoms in an asymmetric trigonal pyramidal geometry with SeÀ Ob onds in the range of 1.685(8)-1.733(8) ,w hich are in agreement with reported metal selenites. [13] Bond valence sum (BVS) calculation results of Bi(1)-Bi(2), Ti (1) and Se(1)-Se(2)c ations are 2. 87-2.92, 4.17, 3.83-4.09, respectively,p rovingt hat their oxidation states are + 3, + 4a nd + 4.…”

Section: Resultsmentioning

confidence: 99%

“…It is worth mentioning that these compounds are the first examples of bismuth d 0 -TM selenites with fluorine elements. Only two bismuthd 0 TM selenites, namely,B i 2 V 2 Se 4 O 16 and Bi 2 Mo 2 Se 2 O 13 ,h ave been reported in the literature. [16] The 3D 13 are condensed into discrete dimers or infinite 1D chains, whereas the polyhedra in bismuth fluoride selenites are isolated, which is confirmed with the bridging capability of oxygen and fluorine atoms.…”

Section: Resultsmentioning

confidence: 99%

“…Only two bismuthd 0 TM selenites, namely,B i 2 V 2 Se 4 O 16 and Bi 2 Mo 2 Se 2 O 13 ,h ave been reported in the literature. [16] The 3D 13 are condensed into discrete dimers or infinite 1D chains, whereas the polyhedra in bismuth fluoride selenites are isolated, which is confirmed with the bridging capability of oxygen and fluorine atoms. [17] Thermal analyses demonstrate that compounds 1-5 are thermally stable up to about 312, 375, 315, 432, and 295 8C, respectively ( Figure 5).…”

Section: Resultsmentioning

confidence: 99%

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Exploration of New Birefringent Crystals in Bismuth d⁰ Transition Metal Selenites

Gong

Kong

et al. 2019

Chemistry A European J

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The first examples of bismuth fluoride selenites with d0‐TM/TeVI polyhedrons, namely, Bi4TiO2F4(SeO3)4 (1), Bi4NbO3F3(SeO3)4 (2), Bi4TeO4F2(TeO3)2(SeO3)2 (3), Bi2F2(MoO4)(SeO3) (4) and Bi2ZrO2F2(SeO3)2 (5) have been successfully synthesized under hydrothermal reactions by aliovalent substitution. The five new compounds feature three different types of structures. Compounds 1–3, containing TiIV, NbV and TeVI respectively, are isostructural, exhibiting a new 3D framework composed of a 3D bismuth oxyfluoride architecture, with intersecting tunnels occupied by d0‐TM/TeVI octahedrons and selenite/tellurite groups. Interestingly, compound Bi4TeO4F2(TeO3)2(SeO3)2 (3) is the first structure containing SeIV and mixed‐valent TeIV/TeVI cations simultaneously. Compound 4 features a new 3D structure formed by a 3D bismuth oxyfluoride network with MoO4 tetrahedrons and selenites groups imbedded in the 1D tunnels. Compound 5 displays a novel pillar‐layered 3D open framework, consisting of 2D bismuth oxide layers bridged by the [ZrO2F2(SeO3)2]6− polyanions. Theoretical calculations revealed that the five compounds displayed very strong birefringence. The birefringence values of compounds 1–3, especially, are above 0.19 at 1064 nm, which are larger than the mineral calcite. Based on the structure and property analysis, it was found that the asymmetric SeO3 groups (and TeO3 in compound 3) displayed the largest anisotropy, compared with the bismuth cations and the d0‐TM/Te polyhedra, which is beneficial to the birefringence.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Exploration of New Birefringent Crystals in Bismuth d⁰ Transition Metal Selenites

Gong

Kong

et al. 2019

Chemistry A European J

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“…Metal selenites and tellurites are widely regarded as excellent candidates for NLO crystals. ,,− Owing to the presence of stereochemically active lone-pairs on the Se 4+ and Te 4+ cations, selenites and tellurites tend to crystallize in noncentrosymmetric (NCS) or polar space groups and exhibit strong second-order polarizability when the lone-pairs are properly aligned . Cations susceptible to second-order Jahn–Teller distortions, such as octahedrally coordinated d 0 transition metals (d 0 TMs, e.g., Ti 4+ , V 5+ , Nb 5+ , W 6+ , Mo 6+ , etc.…”

Section: Introductionmentioning

confidence: 99%

AGa₃F₆(SeO₃)₂ (A = Rb, Cs): A New Type of Phase-Matchable Hexagonal Tungsten Oxide Material with Strong Second-Harmonic Generation Responses

Jiang

Lin

et al. 2020

Chem. Mater.

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Combining a wide band gap, strong secondharmonic generation (SHG), and good phase matchability into a single structure is an ongoing challenge in the design of nonlinear optical (NLO) materials. Herein, we report the first examples of fluorinated gallium selenites AGa 3 F 6 (SeO 3 ) 2 [A = Rb (RGFS), Cs (CGFS)] by introducing fluorinated main-group metal octahedra [GaO 2 F 4 ] into the metal selenite system. The two new compounds are isostructural (noncentrosymmetric space group P6 3 mc) and feature interesting hexagonal tungsten oxide (HTO)-type [Ga 3 F 6 (SeO 3 ) 2 ] ∞ layers, with alkali metal cations acting as linkers between these layers while also maintaining charge balance. Photophysical studies demonstrate that RGFS and CGFS exhibit strong phase-matchable SHG responses [5.6 × KH 2 PO 4 (RGFS) and 5.4 × KH 2 PO 4 (CGFS) at 1064 nm], high laser damage thresholds [39.37 MW/cm 2 (RGFS), 41.59 MW/cm 2 (CGFS) at 1064 nm, 10 ns pulses, 1 Hz repetition rate], wide band gaps [3.57 eV (RGFS), 3.65 eV (CGFS), the latter the highest value among polar HTO-type selenites or tellurites], and large birefringences (0.097 and 0.092 at 546 nm for RGFS and CGFS, respectively); the two compounds simultaneously exhibit multiple key NLO parameters for practical applications in the near-ultraviolet and mid-infrared region. The critical role of the [GaO 2 F 4 ] 5− groups in the linear and NLO responses in the two materials has been elucidated by first-principles studies. Our report demonstrates that introducing fluorinated main-group metal octahedra into metal selenite systems can lead to promising multicomponent selenite NLO materials.

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“…In order to achieve NLO compounds with noncentrosymmetric structures, various advantageous functional building units are involved to generate large SHG intensities [19][20][21][22][23][24][25][26][27][28], which include (i) planar triangle anionic groups with conjugated π configurations such as (BO 3 ) 3-, (CO 3 ) 2 ) with second-order Jahn-Teller (SOJT) distortions. These units or their derivatives can be incorporated to explore new NLO materials in UV/DUV or IR regions.…”

Section: Introductionmentioning

confidence: 99%

Designing excellent mid-infrared nonlinear optical materials with fluorooxo-functional group of d0 transition metal oxyfluorides

et al. 2019

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Exploration of new infrared (IR) nonlinear optical (NLO) materials is still in urgency owing to the indispensable roles in optoelectronic devices, resource exploration, and long-distance laser communication. The formidable challenge is to balance the contradiction between wide band gaps and large second harmonic generation (SHG) effects in IR NLO materials. In the present work, we proposed new kinds of NLO active units, d 0 transition metal fluorooxofunctional groups for designing mid-IR NLO materials. By studying a series of d 0 transition metal oxyfluorides (TMOFs), the influences of fluorooxo-functional groups with different d 0 configuration cations on the band gap and SHG responses were explored. The results reveal that the fluorooxo-functional groups with different d 0 configuration cations can enlarge band gaps in mid-IR NLO materials. The first-principles calculations demonstrate that the nine alkali/alkaline earth metals d 0 TMOFs exhibit wide band gaps (all the band gaps > 3.0 eV), large birefringence Δn (> 0.07), and two W/Mo TMOFs also exhibit large SHG responses. Moreover, by comparing with other fluorooxo-functional groups, it is found that introducing fluorine into building units is an effective way to enhance optical performance. These d 0 TMOFs with superior fluorooxo-functional groups represent a new exploration family of the mid-IR region, which sheds light on the design of mid-IR NLO materials possessing large band gap.

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Li₆M(SeO₃)₄ (M = Co, Ni, and Cd) and Li₂Zn(SeO₃)₂: Selenites with Late Transition-Metal Cations

Cited by 27 publications

References 68 publications

Exploration of New Birefringent Crystals in Bismuth d⁰ Transition Metal Selenites

Exploration of New Birefringent Crystals in Bismuth d⁰ Transition Metal Selenites

AGa₃F₆(SeO₃)₂ (A = Rb, Cs): A New Type of Phase-Matchable Hexagonal Tungsten Oxide Material with Strong Second-Harmonic Generation Responses

Designing excellent mid-infrared nonlinear optical materials with fluorooxo-functional group of d0 transition metal oxyfluorides

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Li6M(SeO3)4 (M = Co, Ni, and Cd) and Li2Zn(SeO3)2: Selenites with Late Transition-Metal Cations

Cited by 27 publications

References 68 publications

Exploration of New Birefringent Crystals in Bismuth d0 Transition Metal Selenites

Exploration of New Birefringent Crystals in Bismuth d0 Transition Metal Selenites

AGa3F6(SeO3)2 (A = Rb, Cs): A New Type of Phase-Matchable Hexagonal Tungsten Oxide Material with Strong Second-Harmonic Generation Responses

Designing excellent mid-infrared nonlinear optical materials with fluorooxo-functional group of d0 transition metal oxyfluorides

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Li₆M(SeO₃)₄ (M = Co, Ni, and Cd) and Li₂Zn(SeO₃)₂: Selenites with Late Transition-Metal Cations

Exploration of New Birefringent Crystals in Bismuth d⁰ Transition Metal Selenites

Exploration of New Birefringent Crystals in Bismuth d⁰ Transition Metal Selenites

AGa₃F₆(SeO₃)₂ (A = Rb, Cs): A New Type of Phase-Matchable Hexagonal Tungsten Oxide Material with Strong Second-Harmonic Generation Responses