Promising Material for Infrared Nonlinear Optics: NaI3O8 Salt Containing an Octaoxotriiodate(V) Anion Formed from Condensation of [IO3]− Ions

Phanon, Delphine; Gautier‐Luneau, Isabelle

doi:10.1002/anie.200703340

Cited by 215 publications

(183 citation statements)

References 33 publications

(32 reference statements)

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“…Many of them have been also reported to be promising new SHG materials with wide transparency wavelength regions, large SHG coefficients and high optical-damage thresholds as well as high thermal stability [19][20][21]. For example, NaI 3 O 8 , containing zero-dimensional I 3 O 8  polyanionic units displays a SHG response that is comparable to that of -LiIO 3 [19], and Cs 2 I 4 O 11 with a HTO-like (hexagonal tungsten oxide) 2D layer of I 4 O 1 2 1  anions shows a SHG efficiency of 300 × -SiO 2 (Figure 1) [20]. So far, a number of ternary metal iodates have been reported, the cations used include alkali, alkaline earth, transition metal, lanthanide, and post-transition metal main group elements [19,20,[24][25][26][27][28][29][30][31][32][33].…”

Section: Introductionmentioning

confidence: 99%

“…As for the metal-oxide-based system, there are mainly two types of inorganic asymmetric units which favor SHG activity, including planar (BO 3 ) 3 with a -conjugated system [14][15][16], and cations subject to second-order Jahn-Teller (SOJT) distorted cations such as octahedrally coordinated d 0 transition metal (TM) cations (e.g. Nb 5+ , V 5+ , Mo 6+ ) [17,18], and lone-pair cations (I 5+ , Se 4+ , Te 4+ , Pb 2+ , Bi 3+ , etc) [19][20][21][22][23]. Because of the SOJT effects, both two types of cations are in asymmetric coordination environments.…”

Section: Introductionmentioning

confidence: 99%

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Structures and properties of functional metal iodates

2011

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Metal iodates with a lone-pair containing I(V) that is in an asymmetric coordination geometry can form a diversity of unusual structures and many of them are promising new second homonic generation (SHG) materials. They exhibit wide transparency wavelength regions, large SHG coefficients and high optical-damage thresholds as well as moderately high thermal stability. In this paper, the structures and properties of the metal iodates are reviewed. The combination of d 0 transition-metal cations with the iodate groups afforded a large number of metal iodates, with cations covering alkali metal, alkaline earth and lanthanide elements. Many of them are noncentrosymmetric (NCS) and display excellent SHG properties due to the additive effects of polarizations from both types of the asymmetric units. Some lanthanide iodates are able to emit strong luminescence in the visible or near-IR regions. The use of transition metal ions with d n (n ≠ 0) electronic configuration into iodate systems can also induce the formation of NCS compounds when the lone pairs of the iodate groups are properly aligned. The d n transition metal cations are normally octahedrally coordinated or in a square-planar coordination geometry. Furthermore, the combination of two different types of lone-pair-containing cations is also an effective strategy to design new SHG materials. second homonic generation (SHG), metal iodates, crystal structures, structure-property relationship

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Structures and properties of functional metal iodates

2011

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“…In order to obtain NLO materials exhibiting strong second-harmonic generation (SHG) effects, a number of methods have been discussed. Combining asymmetric building units, such as distorted octahedra with a d 0 transition metal cation [39][40][41], polyhedra with a d 10 metal cation revealing a polar displacement [42,43], and metal ions with ns 2 lone pair electrons [44] in the frameworks of new materials is a common approach to increase the incidence of many good NLO materials [45,46]. Incorporation of the above mentioned acentric building units into a nitrates system may also enlarge the SHG efficiency of materials.…”

Section: Introductionmentioning

confidence: 99%

Rb2Na(NO3)3: A Congruently Melting UV-NLO Crystal with a Very Strong Second-Harmonic Generation Response

et al. 2016

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Crystals of congruently melting noncentrosymmetric (NCS) mixed alkali metal nitrate, Rb 2 Na(NO 3 ) 3 , have been grown through solid state reactions. The material possesses layers with NaO 8 hexagonal bipyramids and NO 3 triangular units. Rb + cations are residing in the interlayer space. Each NaO 8 hexagonal bipyramid shares its corners and edges with two and three NO 3 units, respectively, in order to fulfill a highly dense stacking in the unit cell. The NaO 8 groups share their six oxygen atoms in equatorial positions with three different NO 3 groups to generate a NaO 6 -NO 3 layer with a parallel alignment. The optimized arrangement of the NO 3 groups and their high density in the structure together produce a strong second-harmonic generation (SHG) response. Powder SHG measurements indicate that Rb 2 Na(NO 3 ) 3 has a strong SHG efficiency of five times that of KH 2 PO 4 (KDP) and is type I phase-matchable. The calculated average nonlinear optical (NLO) susceptibility of Rb 2 Na(NO 3 ) 3 turns out to be the largest value among the NLO materials composed of only [NO 3 ]á nion. In addition, Rb 2 Na(NO 3 ) 3 exhibits a wide transparency region ranging from UV to near IR, which suggests that the compound is a promising NLO material.

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“…Accordingly, NLO behavior is achieved by off-centering of ions in polyhedra or NCS chromophores cooperatively effect in solid-state materials. Here, the chromophore can result from the coordination structure distortion of a d 0 cation with a secondorder Jahn-Tellere effect [17][18][19], polar displacement of d 10 cation centers [20], distortion from a stereochemically active lone pair (SCALP) of cations [21,22], or borate p-orbital systems [23][24][25]. Sometimes, two NCS chromophores occur naturally in the same material [17,[26][27][28].…”

Section: Introductionmentioning

confidence: 98%

Structural Designs and Property Characterizations for Second-Harmonic Generation Materials

Cheng

Lin

Zhang

et al. 2012

Structure-Property Relationships in Non-Linear Optical Crystals I

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Second-harmonic generation (SHG) materials only exist in solids that have no inversion center space groups, and they are constructed by the building blocks or chromophores of noncentrosymmetricity (NCS). In this chapter, we employed one or multiple chromophores that result from the coordination structure distortions of a d 0 cation, polar displacement of d 10 cation center, a stereochemically active lone pair (SCALP) of cations, and asymmetrical delocalization p-charge systems, as building blocks to obtain some new compounds with NCS space group. The single-crystal structures were characterized, and physical properties, in particular SHG responses, were measured for these compounds. The electronic structures and density of states were calculated by DFT method, and the SHG properties are simulated to gain an insight into the relations between structure and NLO properties for the materials. The electronic origination of large SHG responses was assigned in terms of the calculated results.

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Promising Material for Infrared Nonlinear Optics: NaI₃O₈ Salt Containing an Octaoxotriiodate(V) Anion Formed from Condensation of [IO₃]⁻ Ions

Cited by 215 publications

References 33 publications

Structures and properties of functional metal iodates

Structures and properties of functional metal iodates

Rb2Na(NO3)3: A Congruently Melting UV-NLO Crystal with a Very Strong Second-Harmonic Generation Response

Structural Designs and Property Characterizations for Second-Harmonic Generation Materials

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