A new rubidium beryllium borate,RbBe4(BO3)3

Single crystals of a new rubdidium beryllium borate, RbBe₄(BO₃)₃, have been obtained by spontaneous nucleation from a high‐temperature melt. This new ortho­rhom­bic (Pnma) structure type contains [Be₂BO₄]⁻ rings, made of two BeO₄ tetra­hedra and one BO₃ triangle, which constitute the basic structural units. The m plane runs through the B and one of the O atoms and intersects the ring. These rings form chains in the a direction, which are connected in the b and c directions to form zeolite‐type cages in which the Rb⁺ cations are located, at sites of m symmetry.     

Zwei Fluoridborate des Gadoliniums: Gd2F3[BO3] und Gd3F3[BO3]2

Two Fluoride Borates of Gadolinium: Gd₂F₃[BO₃] and Gd₃F₃[BO₃]₂ By flux‐supported solid‐state reaction of Gd₂O₃ and GdF₃ with B₂O₃ (flux: CsCl, molar ratio: 1 : 1 : 1 : 6, sealed tantalum capsule, 700 °C, 7 d) the new gadolinium fluoride borate Gd₂F₃[BO₃] (monoclinic, P2₁/c; a = 1637.2(1), b = 624.78(4), c = 838.04(6) pm, β = 93.341(8)°; V_m = 64.418(6) cm³/mol, Z = 8) was obtained as colourless, prismatic, face‐rich single crystals. The four crystallographically different Gd³⁺ cations (CN = 9) are all capped square‐antiprismatically surrounded by fluoride and oxide anions, in which the latter represent always components of isolated trigonal planar [BO₃]^3— anions. The six crystallographically independent F^— anions all reside in more or less planar coordination of three Gd³⁺ cations. Thus the constitution of Gd₂F₃[BO₃] can be described as a sequence of alternating layers each of the composition Gd[BO₃] and GdF₃ parallel (100), respectively. The crystal structures of Gd₂F₃[BO₃] and the shortly published Gd₃F₃[BO₃]₂ (monoclinic, C2/c; a = 1253.4(1), b = 623.7(1), c = 836.0(1) pm, β = 97.404(6)°; V_m = 97.571(9) cm³/mol, Z = 4) are compared with each other. Due to the structural analogies between these two gadolinium fluoride borates, a disorder model of the boron atoms frequently found for Gd₂F₃[BO₃] is able to be transferred to Gd₃F₃[BO₃]₂ as well.     

A non‐linear optical crystal,Cd3Zn3(BO3)4

The title compound, tricadmium trizinc tetraborate, Cd₃Zn₃(BO₃)₄, is a new non‐linear optical (NLO) crystal and its structure has been determined by single‐crystal X‐ray diffraction. This compound is composed of planar [BO₃]³⁻ groups sharing O atoms with CdO₄ or ZnO₄ tetrahedra. The BO₃ triangles are located on threefold axes and are arranged with nearly the same orientation. The Cd and Zn atoms are disordered on the same site in the proportion 1:1. A strong second harmonic generation of Nd:YAG laser radiation (λ = 1064 nm) has been observed for a crystal of the title compound.     

Pr(BO2)3 und PrCl(BO2)2: Zwei meta‐Borate des Praseodyms im Vergleich

Pr(BO₂)₃ and PrCl(BO₂)₂: Two Praseodymium meta‐Borates in Comparison Single‐crystalline PrCl(BO₂)₂ can be obtained by the reaction of praseodymium, Pr₆O₁₁ and PrCl₃ with a small excess of B₂O₃ in evacuated silica tubes after seven days at 850 °C. If NaCl is additionally used as flux, single crystals of Pr(BO₂)₃ dominate the main product. Both praseodymium(III) meta‐borates are air and water stable. The crystals of PrCl(BO₂)₂ emerge as long, thin, pale green needles which tend to severe twinning due to their fibrous habit. The crystal structure (triclinic, P1¯; a = 420.56(4), b = 655.42(7), c = 808.34(8) pm, α = 82.361(8), β = 89.173(9), γ = 71.980(7)°, Z = 2) exhibits zigzag chains {[(B1)o^t_1/1O^e_2/2(B2)O^t_1/1O^e_2/2]²⁻} (≡ {[BO₂]⁻}) of corner‐linked [BO₃]³⁻ triangles with syndiotactic orientation of the terminal oxygen atoms which are running parallel to the [100] direction. The Pr³⁺ cations are surrounded by three Cl⁻ and seven O²⁻ anions with the shape of a tetracapped trigonal prism. The green, transparent crystals of Pr(BO₂)₃ (monoclinic, C2/c; a= 984.98(9), b = 809.57(8), c = 641.02(6) pm, β = 126.783(9)°, Z = 4) appear either lath‐shaped or rather spherical. In the crystal structure the B³⁺ cations reside both in trigonal planar as well as in tetrahedral coordination of oxygen atoms. Both types of borate polyhedra ([BO₃]³⁻ and [BO₄]⁵⁻) are linked via corners to form chains of the composition {[(B2)‐O^t_1/1O^e_2/2(B1)O^e_4/2(B2)O^t_1/1O^e_2/2]³⁻} (≡ {[BO₂]⁻}) which run parallel [101]. The coordination sphere of the Pr³⁺ cations consists of ten oxide anions which build up a bicapped square antiprism.     

La4B14O27: Ein Lanthan‐ultra‐Oxoborat mit Raumnetzstruktur

La₄B₁₄O₂₇: A Lanthanum ultra‐Oxoborate with a Framework Structure Single crystals of La₄B₁₄O₂₇ could be synthesized by the reaction of La₂O₃, LaCl₃ and B₂O₃ with an access of CsCl as fluxing agent in gastightly sealed platinum ampoules within twenty days at 710 °C and appear as colourless, transparent and waterresistant platelets. The new lanthanum oxoborate La₄B₁₄O₂₇ (monoclinic, C2/c; a = 1120.84(9), b = 641.98(6), c = 2537.2(2) pm, β = 100.125(8)°; Z = 4) is built of a three‐dimensional boron‐oxygen framework containing seven crystallographically different boron atoms. Four of these B³⁺ cations are surrounded by four O^2? anions tetrahedrally, whereas the other three have only three oxygen neighbours with nearly plane triangular coordination figures. Three of the [BO₄]^5? tetrahedra form [B₃O₉]^9? rings by cyclic vertex‐condensation, which are further linked via [BO₃]^3? units to infinite layers. Two of these layers connect via one [B₂O₇]^8? unit of two corner‐shared [BO₄]^5? tetrahedra to double layers, which themselves build up a three‐dimensional framework together with chains consisting of two [BO₄]^5? tetrahedra and one [BO₃]^3? triangle. One of the two crystallographically independent La³⁺ cations (La1) is surrounded by ten O^2? anions and resides within the oxoborate double layers. (La2)³⁺ shows a (8+2)‐fold coordination of O^2? anions and occupies channels along the [110] direction.     

Pb2BO3Cl: A Tailor‐Made Polar Lead Borate Chloride with Very Strong Second Harmonic Generation

A meticulously designed, polar, non‐centrosymmetric lead borate chloride, Pb₂BO₃Cl, was synthesized using KBe₂BO₃F₂ (KBBF) as a model. Single‐crystal X‐ray diffraction revealed that the structure of Pb₂BO₃Cl consists of cationic [Pb₂(BO₃)]⁺ honeycomb layers and Cl^? anions. Powder second harmonic generation (SHG) measurements on graded polycrystalline Pb₂BO₃Cl indicated that the title compound is phase‐matchable (type I) and exhibits a remarkably strong SHG response, which is approximately nine times stronger than that of potassium dihydrogen phosphate, and the largest efficiency observed in materials with structures similar to KBBF. Further characterization suggested that the compound melts congruently at high temperature and has a wide transparency window from the near‐UV to the mid‐IR region.     

[O2Pb3]2(BO3)Br: An Oxidoborate Oxide Bromide with the ∞1[O2Pb3] Double Chains Based on Edge‐sharing OPb4 Tetrahedra

Through extensive research on the PbO / PbBr₂ / B₂O₃ system, a new single crystal of yellow lead‐containing oxyborate bromine, [O₂Pb₃]₂(BO₃)Br, was grown from the melt. It crystallizes in the centrosymmetric space group Cmcm (no. 63) of the orthorhombic system with the following unit cell dimensions: a = 9.5748(8) Å, b = 20.841(2) Å, c = 5.7696(5) Å, and Z = 4. The whole structure is characterized by an infinite one‐dimensional (1D) _∞¹[O₂Pb₃] double chain, which is based on the OPb₄ oxocentered tetrahedra and considered as the derivative of the continuous sheet of OPb₄ tetrahedra from the tetragonal modification of α‐PbO. The 1D _∞¹[O₂Pb₃] double chains are further bridged by the BO₃ units through common oxygen atoms to form two‐dimensional (2D) _∞¹[[(O₂Pb₃)(BO₃)] layers, with Br atoms situated between the layers. IR spectroscopy, UV/Vis/NIR diffuse reflectance spectroscopy, and thermal analysis were also performed on the reported material.     

Synthese und Kristallstruktur von Terbium(III)‐meta‐Oxoborat Tb(BO2)3 (≡ TbB3O6)

Synthesis and Crystal Structure of Terbium(III) meta‐Oxoborate Tb(BO₂)₃ (≡ TbB₃O₆) The terbium meta‐oxoborate Tb(BO₂)₃ (≡ TbB₃O₆) is obtained as single crystals by the reaction of terbium, Tb₄O₇ and TbCl₃ with an excess of B₂O₃ in gastight sealed platinum ampoules at 950 °C after three weeks. The compound appears to be air‐ and water‐resistant and crystallizes as long, thin, colourless needles which tend to growth‐twinning due to their marked fibrous habit. The crystal structure of Tb(BO₂)₃ (orthorhombic, Pnma; a = 1598.97(9), b = 741.39(4), c = 1229.58(7) pm; Z = 16) contains strongly corrugated oxoborate layers {(BO₂)^‐} built of vertex‐linked [BO₄]^5‐ tetrahedra (d(B‐O) = 143 ‐ 154 pm, ?(O‐B‐O) = 102‐115°) which spread out parallel (100). The four crystallographically different Tb³⁺ cations all exhibit coordination numbers of eight towards the oxygen atoms (d(Tb‐O) = 228‐287 pm). The corresponding metal cation polyhedra [TbO₈]¹³⁺ too convene to layers (composition: {(Tb₂O₁₁)^16‐}) which are likewise oriented parallel to the (100) plane.     

High-temperature synthesis, single-crystal X-ray structure determination and solid-state NMR investigations of Ba7[SiO4][BO3]3CN and Sr7[SiO4][BO3]3CN

The novel alkaline earth silicate borate cyanides Ba₇[SiO₄][BO₃]₃CN and Sr₇[SiO₄][BO₃]₃CN have been obtained by the reaction of the respective alkaline earth metals M=Sr, Ba, the carbonates M^IICO₃, BN, and SiO₂ using a radiofrequency furnace at a maximum reaction temperature of 1350°C and 1450°C, respectively. The crystal structures of the isotypic compounds M^II₇[SiO₄][BO₃]₃CN have been determined by single-crystal X-ray crystallography (P6₃mc (no. 186), Z=2, a=1129.9(1) pm, c=733.4(2) pm, R₁=0.0336, wR₂=0.0743 for M^II=Ba and a=1081.3(1) pm, c=695.2(1) pm, R₁=0.0457, wR₂=0.0838 for M^II=Sr). Both ionic compounds represent a new structure type, and they are the first examples of silicate borate cyanides. The cyanide ions are disordered and they are surrounded by Ba²⁺/Sr²⁺ octahedra, respectively. These octahedra share common faces building chains along [001]. The [BO₃]³⁻ ions are arranged around these chains. The [SiO₄]⁴⁻ units are surrounded by Ba²⁺/Sr²⁺ tetrahedra, respectively. The title compounds additionally have been investigated by ¹¹B, ¹³C, ²⁹Si, and ¹H MAS-NMR as well as IR and Raman spectroscopy confirming the presence of [SiO₄]⁴⁻, [BO₃]³⁻, and CN⁻ ions.     

Ba3(BO3)(CO3)F: The First Borate Carbonate Fluoride Synthesized by the High-Temperature Solution Method

In contrast to the well-investigated halogen-containing borates and carbonates, very few halogen-containing borate carbonate compounds have been reported. Specifically, no example of borate carbonate fluoride has been synthesized successfully until now. Herein, the planar π-conjugated units [BO₃]³⁻ and [CO₃]²⁻ and the F⁻ ions are introduced simultaneously into one crystal structure resulting in the first borate carbonate fluoride, Ba₃(BO₃)(CO₃)F, by the high-temperature solution method in the atmosphere. Its structure features a hexagonal channel formed by the [BO₃]³⁻ and [CO₃]²⁻ units with the [F₃Ba₈]¹³⁺ trimers filled in the channel. Various characterizations including single crystal- and powder-XRD, EDX, IR, UV-vis-NIR, and TG-DSC, together with the first principles calculation have been carried out to verify the structure and fully understand the structure–property relationships.     

Mixed Alkali Neodymium Orthoborates: K9Li3Nd3(BO3)7 and A2LiNd(BO3)2 (A = Rb,Cs)

Crystals of mixed alkali neodymium orthoborates, K₉Li₃Nd₃(BO₃)₇ and A₂LiNd(BO₃)₂ (A = Rb, Cs) were obtained by spontaneous crystallization. K₉Li₃Nd₃(BO₃)₇ crystallizes in space group P2/c with cell parameters of a = 11.4524(7) Å, b = 10.1266(6) Å, c = 12.3116 (10) Å, β = 122.0090(10)°. In the structure, NdO₈ polyhedra share corners and connect with planer BO₃ groups to form infinite [Nd₃B₃O₂₁]_n chains. These chains are linked by additional BO₃ groups to produce a double layer of [Nd₆B₆O₃₈]_n blocks in the ac plane with K and Li ions filled into the cavities. A₂LiNd(BO₃)₂ (A = Rb, Cs) crystallizes in space group Pbcm, with cell parameters of a = 7.113(2) Å, b = 9.691(3) Å and c = 10.135(3) Å for Rb₂LiNd(BO₃)₂, and a = 7.2113(3) Å, b = 9.9621(4) Å, and c = 10.3347(4) Å for Cs₂LiNd(BO₃)₂. In the structure, NdO₈ polyhedra are corner‐sharing with each other and further interlinked by BO₃ groups to comprise the infinite [Nd₄B₄O₂₄] sheets in the bc plane, with Rb/Cs and Li ions occupying the interlayered space. The compounds show effective near‐IR emission and their associated lifetimes are obtained by fluorescence spectra.     

A New Sodium Borate: Na[B6O8(OH)3]·6H2O·H3BO3

The structure of [B₆H₉NaO₁₄, H₃BO₃, 6H₂O] was determined by single‐crystal X‐ray diffraction and further analyzed by FTIR spectroscopy and differential thermal/thermogravimetric analysis. The asymmetric unit contains Na–O polyhedra (distorted octahedron), [B₆O₈(OH)₃]^– fundamental building blocks, one free water molecule and one free H₃BO₃ molecule. In the hexaborate anion, three B₃O₃ rings are linked by a common oxygen atom with five trigonal and one tetrahedral boron atoms. The hexaborate group is also linked to the oxygenated environment of the sodium atom by three other six‐membered rings, each of which involve two boron atoms, three oxygen atoms, and sodium as the joint atom.     

An alkoxide cluster with 18 Li+ ions encapsulating two borate anions, [(tBuO)12Li18(BO3)2]

The title compound, bis­(borato)­dodeca(tert‐butoxo)­octa­deca­lithium, [Li₁₈(BO₃)₂(C₄H₉O)₁₂], is formulated conveniently as [{(^tBuOLi)₃(Li₃BO₃)}₂(^tBuOLi)₆]. A central 12‐membered ring and two outer six‐membered rings are formed by alternating Li⁺ cations and alkoxide O atoms. Sandwiched between the central ring and each of the outer rings is a planar array of three further Li⁺ cations surrounding a [BO₃]³⁻ anion. Thus, the mol­ecule consists of a cationic [Li₁₈(O^tBu)₁₂]⁶⁺ cage encapsulating two borate anions. This compound is the first example of a structurally characterized polynuclear lithium borate, and a rare case of a lithium alkoxide cage with nuclearity greater than eight. All the alkoxide ligands are triply bridging, and the lithium ions have trigonal‐planar, trigonal‐pyramidal and fourfold coordination, all with major distortions from regular coordination geometry.     

A Facile Synthetic Route to a New SHG Material with Two Types of Parallel π‐Conjugated Planar Triangular Units

A new SHG material, namely, Pb₂(BO₃)(NO₃), which contains parallel π‐conjugated nitrate and borate anions, was obtained through a facile hydrothermal reaction by using Pb(NO₃)₂ and Mg(BO₂)₂?H₂O as starting materials. Its structure contains honeycomb [Pb₂(BO₃)]_∞ layers with noncoordination [NO₃]^? anions located at the interlayer space. Pb₂(BO₃)(NO₃) shows a remarkable strong SHG response of approximately 9.0 times that of potassium dihydrogen phosphate (KDP) and the material is also phase‐matchable. The large SHG coefficient of Pb₂(BO₃)(NO₃) arises from the synergistic effect of the stereoactive lone pairs on Pb²⁺ cations and parallel alignment of π‐conjugated BO₃ and NO₃ units. Based on its unique properties, Pb₂(BO₃)(NO₃) may have great potential as a high performance NLO material in photonic applications.     

Prediction of Fluorooxoborates with Colossal Second Harmonic Generation (SHG) Coefficients and Extremely Wide Band Gaps: Towards Modulating Properties by Tuning the BO3/BO3F Ratio in Layers

Fluorooxoborates have inspired investigations of deep‐ultraviolet (DUV) nonlinear optical (NLO) materials that can meet the multiple criteria. Herein, five stable structures with the composition of BaB₂O₃F₂ (I–V) are discovered using the ab initio evolutionary algorithm. Among them, BaB₂O₃F₂‐I has been synthesized experimentally and confirms the reliability of the method. All of the predicted structures possess extremely wide band gaps (8.1–9.0 eV). Moreover, four new structures exhibit giant second harmonic generation (SHG) coefficients (>3×KDP, d₃₆=0.39 pm V^?1). A novel type of the [BOF] layer with BO₃:BO₃F ratio of [1:1] is found in BaB₂O₃F₂‐II and BaB₂O₃F₂‐III. While BaB₂O₃F₂‐IV and BaB₂O₃F₂‐V are solely composed of the BO₃F group and have colossal SHG coefficients (ca. 4×KDP). It gives the direct evidence that the BO₃F group could generate strong SHG effect. Most importantly, the influences of BO₃:BO₃F ratio and their number density on band gap, birefringence and SHG effects are investigated.     

Preparation of Li_(4.4)Al_(0.4)Si_(0.6)O_4-xLi_3BO_3 Solid Electrolytes by Sol-Gel Method and Their Ionic Conductivity

Ｉｎｔｒｏｄｕｃｔｉｏｎ　　ＩｎｔｈｅｓｅａｒｃｈｆｏｒｎｅｗＬｉ+ ｉｏｎｃｏｎｄｕｃｔｉｎｇｓｏｌｉｄｓｗｉｔｈｐｏｔｅｎｔｉａｌａｐｐｌｉｃａｔｉｏｎｓａｓｓｏｌｉｄｅｌｅｃｔｒｏｌｙｔｅｓｉｎｈｉｇｈ ｅｎｅｒｇｙｄｅｎｓｉｔｙｂａｔｔｅｒｉｅｓ ,ｃｏｎｓｉｄｅｒａｂｌｅｗｏｒｋｈａｓｂｅｅｎｄｏｎｅｏｎａｖａｒｉｅｔｙｏｆＬｉ+ ｉｏｎｅｌｅｃｔｒｏｌｙｔｅｓ .Ｌｉ4 ＳｉＯ4 ｂａｓｅｄｓｏｌｉｄｓｏｌｕ ｔｉｏｎｓａｒｅｗｅｌｌｋｎｏｗｎｆｏｒｔｈｅｉｒｇｒｅａｔｉｎｃｒｅａｓｅｉｎｃｏｎ…     

Rb3Ti3Te11

Trirubidium trititanium undecatelluride, Rb₃Ti₃Te₁₁, has been synthesized from the reaction of titanium, tellurium, and Rb₂Te₃ at 773 K. Its structure has been determined from single‐crystal X‐ray data. It is composed of one‐dimensional [Ti₃Te₁₁^3?] chains built by face‐sharing pentagonal TiTe₇ bipyramids and distorted TiTe₆ octahedra. These chains adopt hexagonal closest packing along the [101] direction. Rb atoms are located among these chains. The wide range of Te—Te interactions makes the assignment of formal oxidation states impossible. The compound is isostructural with Cs₃Ti₃Te₁₁.     

ChemInform Abstract: YCa3(CrO)3(BO3)4: A Cr3+ Kagome Lattice Compound Showing No Magnetic Order Down to 2 K.

Polycrystalline gaudefroyite‐type YCa₃(CrO)₃(BO₃)₄ with Cr³⁺ ions (3d³, S = 3/2) forming an undistorted Kagome lattice is prepared by reaction of a stoichiometric mixture of Y₂O₃, CaCO₃, Cr₂O₃, H₃BO₃ in a KCl flux (Al₂O₃ crucible, 1000 °C, 1 d) followed by re‐grinding and further annealing (1000 °C, 2 d, 95% yield).     

HP‐CsB5O8: Synthesis and Characterization of an Outstanding Borate Exhibiting the Simultaneous Linkage of All Structural Units of Borates

The new cesium pentaborate HP‐CsB₅O₈ is synthesized under high‐pressure/high‐temperature conditions of 6 GPa and 900 °C in a Walker‐type multianvil apparatus. The compound crystallizes in the orthorhombic space group Pnma (Z=4) with the parameters a=789.7(1), b=961.2(1), c=836.3(1) pm, V=0.6348(1) nm³, R₁=0.0359 and wR₂=0.0440 (all data). The new structure type of HP‐CsB₅O₈ exhibits the simultaneous linkage of trigonal BO₃ groups, corner‐sharing BO₄ tetrahedra, and edge‐sharing BO₄ tetrahedra including the presence of threefold‐coordinated oxygen atoms. With respect to the rich structural chemistry of borates, HP‐CsB₅O₈ is the second structure type possessing this outstanding combination of the main structural units of borates in one compound. The structure consists of corrugated chains of corner‐ and edge‐sharing BO₄ tetrahedra interconnected through BO₃ groups forming octagonal channels. Inside these channels, cesium is 13+3‐fold coordinated by oxygen atoms. ¹¹B MQMAS NMR spectra are analyzed to estimate the isotropic chemical shift values and quadrupolar parameters. IR and Raman spectra are obtained and compared to the calculated vibrational frequencies at the Γ‐point. The high‐temperature behavior is examined by means of temperature‐programmed powder diffraction.     

Structure, thermal stability and properties of Li3Sc(BO3)2

Polycrystalline Li₃Sc(BO₃)₂ was synthesized through the solid-state reaction, which is air-, water- and thermal-stable below about 929 °C. Its crystal structure was resolved and refined on the basis of powder X-ray diffraction data. The metal-borate framework is built up from ScO₆ octahedra connected to each other by sharing common edges, corners and faces of BO₃ units and LiO₄ groups. Coordination surrounding of B-O in this structure, [BO₃]³⁻ group, was confirmed by an infrared absorption spectrum of an Li₃Sc(BO₃)₂. According to the electronic structure calculated by first-principles calculations, an Li₃Sc(BO₃)₂ is an insulator with a wide indirect energy band gap of about 4.4 eV. Considering the facile synthesis, large band gap, and thermal stability and excellent Tb³⁺-doped photoluminescence characteristics of this compound in general, it may be a good candidate as host of phosphors deposited on chip of the light-emitting diodes for white-color conversion.