Rb3VO(O2)2CO3: A Four‐in‐One Carbonatoperoxovanadate Exhibiting an Extremely Strong Second‐Harmonic Generation Response

Zou, Guohong; Jo, Hongil; Lim, Seong‐Ji; You, Tae‐Soo; Ok, Kang Min

doi:10.1002/anie.201804354

Cited by 176 publications

(49 citation statements)

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“…Our studies propose that three-site aliovalent substitution is af acile route for the discovery of good NLO materials.Noncentrosymmetric (NCS) oxide materials have extensively excited academic interest owing to their probable properties with applications in second-order nonlinear optics (NLO) as well as in pyroelectrics,f erroelectrics,a nd piezoelectrics. [1][2][3][4][5][6] To the best of our knowledge,a ne xcellent second-order NLO material should feature al arge second harmonic generation (SHG) coefficient, ahigh relevant laserinduced damage threshold (LDT), appropriate optical transmittance range,m oderate birefringence for achieving phase matching,and good thermal stability.Inaddition, it should be free of moisture and accessible by af acile synthetic method. [7][8][9] Metal iodates currently attract extensive research interest due to their potential outstanding SHG response.…”

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A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions

et al. 2019

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Tw om ixed-metal gallium iodate fluorides,n amely, a-and b-Ba 2 [GaF 4 (IO 3 ) 2 ](IO 3 )(1 and 2), have been designed by the aliovalent substitutions of a-a nd b-Ba 2 [VO 2 F 2 (IO 3 ) 2 ]-(IO 3 )( 3 and 4)i nvolving one cationic and two anionic sites. Both 1 and 2 display large second-harmonic generation responses ( % 6 KH 2 PO 4 (KDP)), large energy band gaps (4.61 and 4.35 eV), wide transmittance ranges ( % 0.27-12.5 mm), and high relevant laser-induced damage thresholds (29.7 and 28.3 AgGaS 2 ,r espectively), whichi ndicates that 1 and 2 are potential second-order nonlinear optical materials in the ultraviolet to mid-infrared. Our studies propose that three-site aliovalent substitution is af acile route for the discovery of good NLO materials.Noncentrosymmetric (NCS) oxide materials have extensively excited academic interest owing to their probable properties with applications in second-order nonlinear optics (NLO) as well as in pyroelectrics,f erroelectrics,a nd piezoelectrics. [1][2][3][4][5][6] To the best of our knowledge,a ne xcellent second-order NLO material should feature al arge second harmonic generation (SHG) coefficient, ahigh relevant laserinduced damage threshold (LDT), appropriate optical transmittance range,m oderate birefringence for achieving phase matching,and good thermal stability.Inaddition, it should be free of moisture and accessible by af acile synthetic method. [7][8][9] Metal iodates currently attract extensive research interest due to their potential outstanding SHG response. [10] Up to now,several effective synthetic routes have been reported for exploring the NCS metal iodates featuring novel crystal structures and remarkable SHG performance,s uch as condensing IO 3 À and IO 4 3À units to form polyiodates, [11][12][13] combining six-or five-coordinate d 0 transition metal (TM) cations (e.g.T i 4+ ,V 5+ ,M o 6+ ,a nd Nb 5+ ) [14][15][16][17][18][19][20][21][22] or metal cations (e.g. Bi 3+ and Pb 2+ ) [23][24][25][26] having as tereochemically active lone-pair (SCALP) with iodates,a nd introducing fluoride anions into iodates. [27][28][29][30][31][32] Anumber of excellent SHG materials have been discovered, for instance,NaI 3 O 8 , [11] Cs 2 I 4 O 11 , [13] Li 2 M(IO 3 ) 6 (M = Ti 4+ ,Sn 4+ ,Ge 4+ ), [33][34][35] A(VO) 2 O 2 (IO 3 ) 3 (A = K, Rb,C s, NH 4 ), [15,20] AMoO 3 IO 3 (A = Rb,C s), [14] BaNbO-(IO 3 ) 5 , [17] BiOIO 3 , [23] PbPt(IO 3 ) 6 , [25] Bi(IO 3 )F 2 , [28] and KBi 2 -(IO 3 ) 2 F 5 , [30] which can produce very strong SHG effects (> 10 KH 2 PO 4 (KDP)).Recently,anumber of new NCS crystals were obtained by the aliovalent substitution of known parent compounds to produce materials with strong SHG response. [36][37][38][39][40][41] For example,S e IV O 3 2À has typically been used as as urrogate for I V O 3 À ,w ith substitution of the oxo anion by ah alide anion (usually fluoride anion) to maintain charge balance.T he first bismuth selenite fluoride,B iFSeO 3 ,w ith the strongest SHG performance of all metal selenites,was designed by aliovalent substitution of laye...

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“…owever,t here are some differences between the coordination geometries at the two Ba atoms (Figures S5 and S6). In 1,Ba(1) is coordinated by six Fatoms and five Oatoms from four IO3 …”

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A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions

et al. 2019

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“…Recently, it has been reported that several peroxides exhibit exceptionally strong second-order nonlinear optical responses. [15] It was also proposed that the localized p-conjugated O 2 2À units make considerable contributions to the overall nonlinear optical responses. [15] However, the birefringence values of these peroxides were not measured.…”

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“…[15] It was also proposed that the localized p-conjugated O 2 2À units make considerable contributions to the overall nonlinear optical responses. [15] However, the birefringence values of these peroxides were not measured. As we know, birefringence belongs to the first-order optical response that frequently has a robust positive correlation with the second-order optical response of a crystal.…”

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An Exceptional Peroxide Birefringent Material Resulting from d–π Interactions

Liu

Zhao

et al. 2020

Angew Chem Int Ed

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Birefringent materials, which can modulate the polarization of light, are almost exclusively limited to oxides. Peroxides have long been overlooked as birefringent materials, because they are usually not stable in air. Now, the first peroxide birefringent material Rb 2 VO(O 2 ) 2 F is reported, the single crystals of which keep transparency after being exposed in the air for two weeks. Interestingly, Rb 2 VO(O 2 ) 2 F does not feature an optimal anisotropic structure, but its birefringence (Dn = 0.189 at 546 nm) exceeds those of the majority of oxides. According to the first-principles calculations, this exceptional birefringence should be attributed to the strong electronic interactions between localized p orbital of O 2 2À anions and V 5+ 3d orbitals, which may be also favorable to the stability in the air for Rb 2 VO(O 2 ) 2 F. These findings distinguish peroxides as a brand-new class of birefringent materials that may possess birefringence superior to the traditional oxides.Birefringent materials can modulate the polarization of light, which is among the most interesting phenomena in nature and has resulted in a lot of discoveries, and thus they have attracted a lot of commercial and academic interest in many scientific and engineering branches. [1] Over the past decades, scientists have made continuous intense studies, thereby leading to a variety of commercial birefringent crystals including YVO 4 , [2] LiNbO 3 , [3] rutile (TiO 2 ), [4] calcite (CaCO 3 ), [5] and a-BaB 2 O 4 , [6] which are widely used in optical devices, such as optical isolators, circulators, beam displacers, and phase compensators. [7] Nevertheless, natural birefringent crystals (such as calcite [5] and rutile [4] ) have limited applications because of their poor crystal quality and various geological impurities, while artificial birefringent crystals (for example, YVO 4 , [2] LiNbO 3 , [3] a-BaB 2 O 4[6] ) are relatively expensive and it is energy-consuming to grow their single crystals. Therefore, there is still great demand for outstanding birefringent materials for which it is facile to grow single crystals.It is well-known that birefringence is closely related to the anisotropic polarizability of a structure. [8] Large anisotropic polarizability in crystals will give rise to large birefringence. Some strategies have been developed to enhance the birefringence of a crystal: 1) Introducing second-order Jahn-Teller distorted polyhedra with d 0 cation (V 5+ , Mo 6+ ) centers; [9] related compounds include YVO 4 (Dn = 0.225 at 633 nm) [2] and NaCa 4 V 5 O 17 (Dn = 0.1 at 1064 nm); [10] 2) introduction or condensation of delocalized p-conjugated planar groups such as BO 3 groups; for example, Pan and co-authors recently reported two borates, Li 2 Na 2 B 2 O 5[8b] and CaB 2 O 4 , [8a] which are composed of condensed B 2 O 5 dimers and [B 2 O 4 ] 1 infinite chains and exhibit large birefringences of Dn = 0.095 at 532 nm and Dn = 0.1355 at 546 nm, respectively; 3) introducing highly polarizable cations such as Hg 2+ with d 10configurati...

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“…Attributed to the nature's symmetry preference, major forms of naturally occurring and synthetically obtained crystalline materials are centrosymmetric. Thus far, however, several NCS chromophores that can facilitate macroscopic NCS space groups have been successfully proposed, which includes (1) two families of cations with second‐order Jahn–Teller distortions, namely, asymmetric lone pair cations and d 0 transition metal cations, (2) highly polarizable d 10 transition metal ions, and (3) anions in trigonal structures with π‐delocalized electrons such as nitrates, carbonates, and borates . Among them, a variety of interesting UV or deep‐UV NLO materials have been recently developed from π‐orbital anionic groups .…”

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Na₂Mg_1−xZn_xSiO₄ (0 ≤ x ≤ 1): Noncentrosymmetric Sodium Metal Silicate Solid Solutions with Ultraviolet Nonlinear Optical Properties

Lee

2019

Bulletin Korean Chem Soc

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Stoichiometrically equivalent noncentrosymmetric (NCS) sodium metal silicates, Na2MgSiO4 and Na2ZnSiO4, and their solid solutions have been synthesized via solid‐state reactions. The structures of the reported materials were determined by powder X‐ray diffraction using the Rietveld method. A careful structural analysis indicates that the unit cell volumes of Na2Mg1−xZn xSiO4 solid solutions decrease as more Zn2+ cations are doped into the site of Mg2+. Also, the synthesized silicate solid solutions revealed three‐dimensional frameworks consisting of highly distorted yet well‐aligned MgO4 (or ZnO4) and SiO4 tetrahedra. The title compounds exhibit very large band gaps ranging from 5.57 to 6.05 eV. Second‐harmonic generation (SHG) measurements indicate that the solid solutions are phase‐matchable and the SHG efficiencies increase as more d10 cation, Zn2+, is added to the backbone. A complete characterization is presented along with the explanation of the structure‐SHG property relationship.

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Rb₃VO(O₂)₂CO₃: A Four‐in‐One Carbonatoperoxovanadate Exhibiting an Extremely Strong Second‐Harmonic Generation Response

Cited by 176 publications

References 42 publications

A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions

A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions

An Exceptional Peroxide Birefringent Material Resulting from d–π Interactions

Na₂Mg_1−xZn_xSiO₄ (0 ≤ x ≤ 1): Noncentrosymmetric Sodium Metal Silicate Solid Solutions with Ultraviolet Nonlinear Optical Properties

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Rb3VO(O2)2CO3: A Four‐in‐One Carbonatoperoxovanadate Exhibiting an Extremely Strong Second‐Harmonic Generation Response

Cited by 176 publications

References 42 publications

A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions

A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions

An Exceptional Peroxide Birefringent Material Resulting from d–π Interactions

Na2Mg1−xZnxSiO4 (0 ≤ x ≤ 1): Noncentrosymmetric Sodium Metal Silicate Solid Solutions with Ultraviolet Nonlinear Optical Properties

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Rb₃VO(O₂)₂CO₃: A Four‐in‐One Carbonatoperoxovanadate Exhibiting an Extremely Strong Second‐Harmonic Generation Response

Na₂Mg_1−xZn_xSiO₄ (0 ≤ x ≤ 1): Noncentrosymmetric Sodium Metal Silicate Solid Solutions with Ultraviolet Nonlinear Optical Properties