BaB2O3F2: A Barium Fluorooxoborate with a Unique [B2O3F]− Layer and Short Cutoff Edge

Substitution of oxygen by fluorine in the borate group offers a materials platform from which intriguing structure and functionality may arise. Herein, we report a new fluorooxoborate, BaB₂O₃F₂, synthesized by introducing the F atoms into the BaO–B₂O₃ system. BaB₂O₃F₂ exhibits a unique oxyfluoride layer [B₂O₃F]⁻ and a deep-ultraviolet cutoff edge below 180 nm. The effect of the introduction of F atoms on the structure and optical property of the borate group has been investigated; this should be useful to further expand borate chemistry and materials.     

Synthesis,Structure and Thermodynamic Property of a New Lithium Borate: Li4[B8O13(OH)2]·3H2O

A new hydrated lithium borate, Li₄[B₈O₁₃(OH)₂]·3H₂O, has been hydrothermally synthesized and characterized by single crystal X‐ray diffraction, FT‐IR spectroscopy, simultaneous TGA‐DTA and chemical analysis. It crystallizes in the triclinic, space group , a=8.4578(5) Å, b=8.7877(5) Å, c=10.8058(7) Å, α=87.740(3)°, β=71.819(3)°, γ=61.569(3)°, Z=2, V=665.26(7) ų, D_c=2.043 g/cm³. Its crystal structure features polyborate anionic layers with the larger odd 13‐membered boron rings constructed by [B₈O₁₃(OH)₂]^4? FBBs. Through designing the thermochemical cycle, the standard molar enthalpy of formation of this borate was determined to be ?(7953.8±6.6) kJ·mol^?1 by using a heat conduction microcalorimeter.     

NaRbB3O4F3: A New Fluorooxoborate with a Short UV Cutoff Edge Enriching the Structural Chemistry of Borate

The combination of RbB₃O₄F₂ and NaF generates a new member of fluorooxoborates, NaRbB₃O₄F₃, with a wide transparency range from the IR to DUV region. NaRbB₃O₄F₃ shows a three-dimensional (3D) structure composed of 1D [B₃O₄F₃]_∞ chains, [NaO₃F₃] and [RbO₅F₅] polyhedra. The structural evolution from NaRbB₃O₄F₃ to RbB₃O₄F₂, as well as the structural comparison between NaRbB₃O₄F₃ and its identical stoichiometry compound, Li₂B₃O₄F₃ were discussed in detail. The IR spectrum verifies its structural validity. The spectral measurement shows that the reflectance has no obvious change in the range of 175–300 nm, and its cutoff edge is below 175 nm. In addition, theoretical calculations are carried out to understand its electronic structure and optical properties.     

A novel mixed-metal borate with large [B12O18(OH)6]6- motif: Synthesis,structure and property

A new mixed-metal polyborate, Na₅Li[B₁₂O₁₈(OH)₆]·2H₂O (1), has been synthesized using solvothermal method and characterized by IR spectroscopy, thermogravimetric analysis, UV–Vis spectroscopy, powder and single-crystal X-ray diffraction, respectively. It crystallizes in the trigonal space group R-3c (No. 167) with unit cell parameters of a = b = 9.6767(6) Å, c = 36.358(5) Å, and Z = 6. Its structure features unprecedented 3D framework constructed from novel honeycomb-shaped inorganic Na-O sheets with unique 12-MR sodium rings and supramolecular polyborate 2D layers of lithium-centered [B₁₂O₁₈(OH)₆]^6-. UV–Vis spectral characterization indicates that compound 1 is a wide-band-gap semiconductor.     

Synthesis, molecular and crystal structure, and features of the electronic structure of bis(O’i)-chelated bis(2,2-dimethylbenzo-[2H]-4-oxo-1,3-oxazino-3-methyl)difluorosilane

A method has been developed for the synthesis of a bis(O→Si)-chelated bis(2,2-dimethylbenzo[2H]-4-oxo-1,3-oxazino-3-methyl)difluorosilane from 2,2-dimethyl-3-trimethylsilylbenzo[2H]-1,3-oxazin-4-one and bis(chloromethyl)dichlorosilane via the intermediate formation of the corresponding unstable bis-chelated dichloride, subsequent hydrolysis with NaHCO₃ and, without separation, treatment of the hydrolysis product with boron trifluoride etherate. Analysis of the electron density distribution showed the presence of dative bonding in both O→Si-F fragments. Dedicated to Prof. Edmunds Lukevics on the occasion of his 70th birthday __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1866–1879, December, 2006.     

Na6[B18Se17]: The First Selenoborato‐closo‐dodecaborate with a Polymeric Chain Anion

Systematic studies on selenoborates containing a B₁₂ cluster entity and alkali metal cations led to the new crystalline phase Na₆[B₁₈Se₁₇] which consists of a icosahedral B₁₂ cluster completely saturated with trigonal‐planar BSe₃ units and sodium counter‐ions. Neighbouring cluster entities are connected in one direction via exocyclic selenium atoms forming the infinite chain anion ([B₁₈Se₁₆Se_2/2]^6–)_∞. The new chalcogenoborate was prepared in a solid state reaction from sodium selenide, amorphous boron and selenium in evacuated carbon coated silica tubes at a temperature of 850 °C. Na₆[B₁₈Se₁₇] crystallizes in the monoclinic space group C2/c (no. 15) with a = 18.005(4) Å, b = 16.549(3) Å, c = 11.245(2) Å, β = 91.35(3)° and Z = 4.     

(enH_2)_4Na_4H_3[(VO)_(12)O_6B_(18)O_(42)]·8H_2O的水热合成和晶体结构

在水热的条件下合成了多钒硼酸盐(enH2)4Na4H3[(VO)12O6B18O42]8H2O, 化学式为C8H59B18N8Na4O68V12 (Mr=2253.45), 用单晶X射线衍射方法测定了它的结构, 该晶体属单斜晶系, P21/n空间群, 晶胞参数为a = 13.8989(4), b = 16.1954(5), c = 14.4520(4) ?β = 94.7490(5), V= 3241.95(16) ?, Z = 2, Dc = 2.308 g/cm3, ?= 1.819mm-1, F(000) = 2234, 4798个可观察衍射点(I > 2s(I)), 最终结构精修到偏离因子R = 0.0449, wR = 0.1163, S = 0.996。在该化合物的结构中, V12B18簇是由环状的B18O42通过18个B(μ3-O)V键被2个V6O18环夹在中间组成的, V12B18簇通过4个Na+与相邻的簇相连, 形成二维网状结构, 孔道尺寸为6.109×10.562 拧?     

The First Example of Inorganic-organic Compound Involving the Largest Vanadium Cluster of [V34O82]10-:Hydrothermal Synthesis and Characterization of a One-dimensional Chain of {[NiC16H36N4]5[V34O82]}n

The title compound, [NiL]5[V34O82·8H2O (1, L=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane), has been synthesized under hydrothermal conditions and structurally characterized by EA, IR, XPS, TG and single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c with a=33.061(4), b=15.3457(17), c=33.902(4), β=101.930(2)°, Mr=4904.08, V=16828(3)3 , Z=4, Dc=1.936 g/cm3 , F(000)=9832, μ=2.425 mm-1 , the final R=0.0402 and wR=0.0969. The mixed valence vanadium clusters of [V34O82]10- bridges [NiL]2+ to form a one-dimensional chain in 1. To the best of our knowledge, the title complex is the first example of organic-inorganic hybrid material involving the largest vanadium cluster of [V34O82]10-.     

新型微孔钨磷多金属氧酸盐(C2N2H10)2[H2P2W18O62]·8H2O的水热合成和电化学性质

采用水热法并以乙二胺为模板剂合成了具有微孔结构的钨磷多金属氧酸盐(C2N2H10)2[H2P2W18O62].8H2O.通过元素分析、等离子发射光谱、X射线单晶衍射等进行了结构表征,并用电化学方法对标题化合物的电化学性质进行了研究.     

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a New Isophthalate- bridged Zinc(II) Polymer with One-dimensional Chain Structure: [Zn(ipt)(im)_2]_(2n)·3nH_2O (ipt = Isophthalate, im = Imidazole)

1 INTRODUCTION The design and synthesis of metal-organic frame- work structure have been studied widely during the past decade not only because of their intriguing architectures but also their unexpected properties for potential practical applications in a wide number of fields, such as asymmetric catalysis, magnetism, pho- toluminescence and so on[1～3]. These novel struc- tures can be rapidly and efficiently synthesized from simple subunits, where the metal ions, bi- or multi- dentate o…     

New Mixed Ligand Organotellurium(IV) Compounds Containing Dithiocarbamates and the More Flexible Imidotetraphenyldithiodiphosphinates. The Crystal Structures of C8H8Te(S2CNEt2)[(SPPh2)2N] · H2O,C8H8Te(S2CNC5H10)[(SPPh2)2N], and C8H8Te(S2CNC4H8S)[(SPPh2)2N]

The synthesis of the following mixed ligand organotellurium(IV) compounds C₈H₈Te(S₂CNEt₂)[(SPPh₂)₂N] · H₂O ( 1 ), C₈H₈Te(S₂CNC₅H₁₀)[(SPPh₂)₂N] ( 2 ), C₈H₈Te(S₂CNC₄H₈O)[(SPPh₂)₂N] ( 3 ) and C₈H₈Te(S₂CNC₄H₈S)[(SPPh₂)₂N] ( 4 ) was achieved. They were characterized by IR, ¹H, ¹³C, ³¹P and ¹²⁵Te NMR, mass spectroscopy, and elemental analyses. The X‐ray crystal structures of 1 , 2 and 4 were determined. The both types of ligands display an asymmetrical chelating coordination mode on interaction with the tellurium atom. When these aniso‐bonded donor atoms are included in the coordination sphere, the tellurium atom exhibit an effective co‐ordination number of seven. The arrangement may be described as 1 : 2 : 2 : 2 coordination with a presumably stereoactive lone‐pair of electrons.     

Synthesis of 1,2,4,5‐Benzenetetrasulfonic Acid (H4B4S) and its Implementation as a Linker for Building Metal‐Organic Frameworks on the Example of [Cu2(B4S)(H2O)8]·0.5H2O

Benzene 1,2,4,5‐tetrasulfonic acid (H₄B4S) was prepared in two steps starting from 1,2,4,5‐Tetrachlorobenzene. Slow evaporation of an aqueous reaction mixture of H₄B4S and Cu₂(OH)₂(CO₃) led to light green single crystals of [Cu₂(B4S)(H₂O)₈] · 0.5H₂O. X‐ray single crystal investigations revealed the compound to be triclinic [P , Z = 1, a = 710.0(1), b = 713.7(1), c = 1077.1(2) pm, α = 98.41(2)°, β = 102.91(2)°, γ = 100.69(2)°]. In the crystal structure the Cu²⁺ ions are coordinated by four water molecules and two monodentate sulfonate anions yielding a tetragonally distorted [CuO₆] octahedron. The anions are connected to further copper ions leading to ladder shaped chains running along the [100] direction. According to DTA/TG investigations the dehydration of the compound is finished at 240 °C and the decomposition of the anhydrous sulfonate starts at 340 °C.     

On Polychalcogenides of Thallium with M2 Q11 Groups as a Structural Building Block. II. Tl4Ta2Se11: Synthesis,Crystal Structure,Properties and Spectroscopic Investigations of the First Polyselenide being Composed of a Discrete [Ta2Se11]4— Anion

The new ternary compound Tl₄Ta₂Se₁₁ was prepared in a melt of thallium polyselenides applying elemental tantalum. It crystallises in the triclinic space group P1¯ with a = 7.996(1) Å, b = 9.866(1) Å, c = 13.668(2) Å, α = 73.03(1)°, β = 89.21(2)° and γ = 85.72(1)°. Tl₄Ta₂Se₁₁ is the first polyselenide with discrete complex [M₂Se₁₁]^4— anions. Every Ta atom is in a sevenfold environment of Se atoms to form a distorted pentagonal bi‐pyramid. The two TaSe₇ polyhedra have a face in common thus yielding the [Ta₂Se₁₁]^4— unit. In the structure, the anions are well separated by the Tl¹⁺ cations. An assignment of the different vibration modes in the IR and Raman spectra is given based on density functional calculations.     

Synthesis and Crystal Structure of a [Mo8O26]4– Cluster Derivative with 4‐MePyH+. First β‐Octamolybdate Derivative with π–π Stacking

Dioxobis(pyridine‐2‐thiolate‐N, S)molybdenum(VI) (MoO₂(Py‐S)₂), reacts with of 4‐methylpyridine (4‐MePy) in acetonitrile, by slow diffusion, to afford the title compound. This has been characterized by elemental analysis, IR and ¹H NMR spectroscopy. The X‐ray single crystal structure of the complex is described. Structural studies reveal that the molecular structure consists of a β‐Mo₈O₂₆ polyanion with eight MoO₆ distorted edge‐shared octahedra with short terminal Mo–O bonds (1.692–1.714 Å), bonds of intermediate length (1.887–1.999 Å) and long bonds (2.150–2.473 Å). Two different types of hydrogen bonds have been found: N–H···O (2.800–3.075 Å) and C–H···O (3.095–3.316 Å). The presence of π–π stacking interactions and strong hydrogen bonds are presumably responsible for the special disposition of the pyridinic rings around the polyanion cluster.     

The First Calcium(II) Complex with the Saccharinate Ligand: Synthesis,Crystal Structure,Spectral and Thermal Characterization of Trans—diaquabis[(2—hydroxyethyl)pyridinium]bis(saccharinato)calcium(II) Disaccharinate, [Ca(sac)2(H2O)2(Hpyet)2](sac)2

A new calcium(II) complex of the saccharinate ligand (sac) with 2—hydroxyethylpyridinium (Hpyet) was synthesized and characterized by elemental analysis, FT—IR spectroscopy, thermal analysis and single crystal X—ray diffractometry. The [Ca(sac)₂(H₂O)₂(Hpyet)₂](sac)₂ complex crystallizes in the triclinic space group (P1¯) with the cell dimensions a = 7.4360(7)Å, b = 12.5263(12)Å, c = 12.8329(13)Å, α = 82.534(8)°, β = 75.202(8)° and γ = 89.662(8)° (293 K). The title complex consists of a complex cation and two sac anions. In the complex cation, the calcium(II) ion is six—coordinate, bonding to two aqua ligands, two Hpyet ligands andtwo sac ligands located in the trans positions. Two of the sac ions are coordinated to the calcium(II) ion through the carbonyl O atom, while the other two remain outside the coordination sphere as the counter—ions. Thermal decomposition of the complex in air results in elimination of aqua, Hpyet, and sac ions, respectively.