High-pressure Synthesis,Structure, IR Spectroscopy,and Theoretical Calculations of the New Silver Tetraborate Ag2B4O7 with a Unique Crystal Structure

Ag₂B₄O₇ is synthesized at high-pressure/high-temperature conditions of 11 GPa and 1073 K in a multianvil device. It crystallizes in the monoclinic centrosymmetric space group P2₁/c (no. 14) with four formula units per unit cell (Z=4). The cell parameters are a=787.53(3), b=651.63(2), c=943.88(3) pm, β=107.911(2)°, and V=460.90(3) ų. Ag₂B₄O₇ crystallizes in a unique crystal structure that consists of complex anionic borate layers with Ag⁺ ions in between. Additionally, the silver cations show argentophilic interactions. The compound was analysed via single-crystal and powder diffraction as well as infrared spectroscopy. Furthermore, theoretical calculations at HSEsol level were conducted.     

Crystal Structure and Properties of a Sodium Terbium Borate Na2.67Tb2.11B3O9

A new nonlinear optical crystal of sodium terbium borate (Na2.67Tb2.11B3O9, Mr=573.14) was synthesized by solid reaction method. The colorless transparent single crystals were grown from the high temperature solution by employing NaBO2 as flux. The structure was determined by single-crystal X-ray diffraction method. The compound crystallizes in the orthorhombic system, space group Amm2 with a=5.0744(10), b=10.990(2), c=6.9078(14) , V=385.24(13) ·3, Dc=4.941 g/cm3, F(000)=250, Z=2, μ=9.205 mm-1, the final R=0.0253 and wR=0.0610. Its three-dimensional network structure is constructed from isolated BO33-, Na(1)O8, Na(2)O6, Na(3)O6 and Tb(1)O9 polyhedra. Variable-temperature magnetic susceptibility measurements show the compound is paramagnetic (μj=7.04 μb). The intensity of the second harmonic generation of Na2.67Tb2.11B3O9 is 2.5 times that of KDP.     

Exploration into the Syntheses of Gallium‐ and Indiumborates under Extreme Conditions: M5B12O25(OH): Structure,Luminescence, and Surprising Photocatalytic Properties

Explorative solid‐state chemistry led to the discovery of the two new compounds Ga₅B₁₂O₂₅(OH) and In₅B₁₂O₂₅(OH). Extreme synthetic conditions within the range of 12 GPa and a temperature of 1450 °C realized in a Walker‐type multianvil apparatus resulted in the formation of an unprecedented tetragonal structure with the exclusive presence of condensed BO₄ tetrahedra, forming cuboctahedral cavities. Doping of these cavities with Eu³⁺ in In₅B₁₂O₂₅(OH) yielded in an orange–red luminescence. Photocatalytic tests of In₅B₁₂O₂₅(OH) revealed a hydrogen production rate comparable to TiO₂ but completely co‐catalyst free.     

Hydrothermal Synthesis and Crystal Structure of a Zinc（Ⅱ） Polymer with a Two-dimensional Layer Structure： [Zn（pzdc）（phen）]n·nH2O

A metal-organic coordination compound formulated as [Zn（pzdc）（phen）]n·nH2O 1 （H2pzdc = pyrazine-2,3-dicarboxylic acid, phen = 1,10-phenanthroline） has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/n with a = 11.607（2）, b = 11.719（2）, c = 13.140（3）A^°, β = 110.707（3）°, V= 1671.9（6）A^°3, C18H12ZnN4O5, Mr= 429.69, De = 1.707 g/cm^3,μ（MoKa） = 1.511 mm^-1, F（000） = 872, Z = 4, the final R = 0.0356 and wR = 0.0853 for 2713 observed reflections （I 〉 2σ（I））. It exhibits an interesting two-dimensional layer structure and shows yellow photoluminescent property at room temperature.     

Synthesis and Crystal Structure of Commensurate Polymorph of Ln4AlCu2B9O23 (Ln=Lu,Ho) and Refinement of Cu2Al6B4O17

Single crystals of new Cu,Lu(Ho)–alumoborate and known Cu,Al–borate were synthesized through reaction between CuB₂O₄ and LnBO₃ on the Al₂O₃ surface by annealing at 1100 °C. Structure of commensurate modification of Ln₄AlCu₂B₉O₂₃, (Ln = Lu,Ho), sp. gr. , was solved at room temperature. It was found that a low–temperature (110 K) modification possesses incommensurate modulations with modulation vector q =(0, 0, 0.132). The nonaborate block – [B₉O₂₃]^19– – 9[6T+3Δ] forms an isolated unique dense closed anionic unit. This block is terminated by Al–tetrahedrons in the chessboard pattern, resulting in formation of complex alumoborate layer [AlB₉O₂₃]^16–. Apical oxygen of central BO₃ triangle of the nonaborate block seems to be the source of modulations observed in low temperature polymorph. Cationic layers with the Ln and Cu atoms are alternating along c axis with anionic layers. The structure Cu₂Al₆B₄O₁₇, previously studied by the Rietveld method, was corroborated by single crystal data and was compared with LiAl₇B₄O₁₇.     

Synthesis,Structure, and Photoluminescence Properties of Novel KBaSc2(PO4)3:Ce3+/Eu2+/Tb3+ Phosphors for White‐Light‐Emitting Diodes

A series of novel KBaSc₂(PO₄)₃:Ce³⁺/Eu²⁺/Tb³⁺phosphors are prepared using a solid‐state reaction. X‐ray diffraction analysis and Rietveld structure refinement are used to check the phase purity and crystal structure of the prepared samples. Ce³⁺‐ and Eu²⁺‐doped phosphors both have broad excitation and emission bands, owing to the spin‐ and orbital‐allowed electron transition between the 4f and 5d energy levels. By co‐doping the KBaSc₂(PO₄)₃:Eu²⁺ and KBaSc₂(PO₄)₃:Ce³⁺ phosphors with Tb³⁺ ions, tunable colors from blue to green can be obtained. The critical distance between the Eu²⁺ and Tb³⁺ ions is calculated by a concentration quenching method and the energy‐transfer mechanism for Eu²⁺→Tb³⁺ is studied by utilizing the Inokuti–Hirayama model. In addition, the quantum efficiencies of the prepared samples are measured. The results indicate that KBaSc₂(PO₄)₃:Eu²⁺,Tb³⁺ and KBaSc₂(PO₄)₃:Ce³⁺,Tb³⁺ phosphors might have potential applications in UV‐excited white‐light‐emitting diodes.     

Synthesis and Characterization of a New Layered Zinc Phosphite (NH4)[{Zn(H2O)4}0.5Zn2(HPO3)3]

A new layered zinc phosphite with the formula (NH₄)[{Zn(H₂O)₄}_0.5Zn₂(HPO₃)₃] has been synthesized under hydrothermal conditions. Its structure was determined by single‐crystal X‐ray diffraction. The compound crystallizes in the triclinic system, space group (No. 2), a = 7.2507(4), b = 9.7982(6), c = 10.2642(6) Å, α = 63.425(2), β = 87.165(2), γ = 72.999(3)°, V = 620.84(6) ų, Z = 2. The connectivity of ZnO₄ tetrahedra, HPO₃ pseudo pyramids and ZnO₂(H₂O)₄ octahedra results in macroanionic layers with 4.8 net.     

Synthesis and Crystal Structure of a Novel Ternary Borate,NaSrB5O9

A novel ternary borate, sodium strontium pentaborate, NaSrB5O9, has been prepared by solid-state reaction below 800 ℃. The single-crystal X-ray structural analysis showed that NaSrB5O9 crystallizes in monoclinic, space group P21/c with a = 6.499(2), b = 13.979(3), c = 8.045(2) , β = 106.92(2)°, V = 699.2(3) 3, Z = 4, Mr = 308.66, Dc = 2.932 g/cm3, μ = 7.804 mm-1, F(000) = 584, R = 0.0264 and wR = 0.0621 for 2426 observed reflections and 146 variables. NaSrB5O9 is a layered compound containing double ring B5O11 building units composed of two BO4 tetrahedra and three BO3 triangles. Each B5O11 unit is connected to four other equivalent units through exocyclic oxygen atoms to form a two-dimensional ∞2 [B5O9]3- layer. Symmetry-center related layers are stacked along the b axis and held together by Na+ and Sr2+ cations via electrostatic interactions.     

三维配位聚合物[Zn（HCO2）2（4,4＇-bipy）]∞的合成、晶体结构及性质研究

以ZnO,HCO2H及4,4-bipy（摩尔比1：3：1.25）溶于H2O和DMF（体积比13：1）,并在60℃反应,合成了标题化合物[Zn（HCO2）2（4,4＇-bipy）∞,对其进行了元素分析、红外光谱等表征,并测定了晶体结构.该化合物晶体属四方晶系,P43212空间群,a=b=0.79675（5）nm,c=1.7627（2）nm,V=1.1190（3）nm^3,Z=4,Dc=1.850 g/cm^3,Mr=311.60,F（000）=632,μ=22.07 cm^-1,最终偏离因子R1=0.0183和wR2=0.0483.该化合物中Zn原子和两个4,4＇-bipy的N原子和四个甲酸根的O原子配位,形成的ZnN2O4八面体通过4,4＇-bipy和甲酸根桥联,组成一种新颖的3D网络结构.同时,研究了该化合物的热性质和荧光性质.     

三维配位聚合物[Zn(HCO2)2(4,4''''-bipy)]∞的合成、晶体结构及性质研究

以ZnO,HCO_2H及4,4'-bipy(摩尔比1∶3∶1.25)溶于H_2O和DMF(体积比13∶1),并在60℃反应,合成了标题化合物[Zn(HCO_2)_2(4,4'-bipy)]_∞,对其进行了元素分析、红外光谱等表征,并测定了晶体结构.该化合物晶体属四方晶系,P4_32_12空间群,a=b=0.79675(5)nm,c=1.7627(2)nm,V=1.1190(3)nm~3,Z=4,Dc=1.850g/cm3,M_r=311.60,F(000)=632,μ=22.07cm-1,最终偏离因子R1=0.0183和wR_2=0.0483.该化合物中Zn原子和两个4,4'-bipy的N原子和四个甲酸根的O原子配位,形成的ZnN_2O_4八面体通过4,4'-bipy和甲酸根桥联,组成一种新颖的3D网络结构.同时,研究了该化合物的热性质和荧光性质.     

Synthesis and Crystal Structure of a Novel Zinc Phosphonate Compound： [Zn（phen）（m-OOCC6H4PO3H）]

A novel zinc（H） metal phosphonate compound [Zn（phen）（m-OOCC6H4PO3H）] 1 （phen = phenanthroline） has been synthesized under hydrothermal conditions. Single-crystal X-ray structure analysis reveals that compound 1 belongs to the triclinic system, space group P1 with a = 9.3356（19）, b = 10.203（2）,c = 10.743（2）A,α = 76.3030（70）, β= 69.2317（51）, y = 84.3833（74）°,V = 929.4（3） ,A3, Z = 2, C2OH15N2O5PZn, Mr = 459.68, Dc = 1.643 g/cm^3,μ= 1.444, mm^-1, F（000） = 468, the final R = 0.0330 and wR = 0.0848. In the structure, the central ion Zn（H） is five-coordinated, linking three O atoms with one from carboxyl and the other two from phosphonyl group. The remained two coordinate sites were occupied by two N atoms from one phen molecule to form the asymmetric unit. Then every two adjacent asymmetric units are bridged by the O atoms from phosphonate group and carboxyl to give rise to a 1D chain along the b axis. These chains are constructed by weak π-π stacking interactions and C-H…π interactions to generate a 3D supramolecular framework.     

Synthesis and Crystal Structure of Zinc Complex [Zn（bipy）3][Zn（SCN）4]

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

4-羧基苯氧乙酸锰配位聚合物[Mn(p-CPOA)(H_2O)_3]_n的合成与晶体结构

0引言由于羧酸化合物具有丰富的配位结构类型,而且羧酸桥联多核配合物广泛存在于生物体内金属蛋白和金属酶的活性部位,使其在配位化学中占有重要地位[1]。尤其是近年来,研究发现羧酸配位聚合物具有潜在的光学、磁学、吸附分离、信息储存以及催化等性能,使得由苯二甲酸,均苯三甲     

一维链状高价锰配合物[Mn_2(C_7H_4O_3)_4(CH_3OH)_2]·4H_2O_2CH_3OH的合成与结构

合成了一维链状高价锰配合物[Mn2(C7H4O3)4(CH3OH)2]4H2O2CH3OH,并对其进行了IR、X-射线衍射、UV-Vis和TG-DSC等表征。单晶衍射结果表明,该配合物晶体属三斜晶型,空间群P?晶胞参数a=7.653(5),b=10.486(7),c=12.943(8),=103.24(1),?=104.55(1),?=110.11(1),V=885.4(9)3,Z=1。UV-Vis光谱在547nm有一个吸收峰,相应于Mn(Ⅳ)的d-d电子跃迁光谱。     

Zinc Hydrazides and Alkoxyhydrazides: Organometallic Compounds with Novel Zn4N8, Zn4N6O and Zn4N4O2 Cage Structures

Tetrameric [{RZn(NHNMe₂)}₄] (R = Me, Et), the first organometallic zinc hydrazides to be described, have been prepared by alkane elimination from dialkylzinc solutions and N,N‐dimethylhydrazine. They were characterised by ¹H and ¹³C NMR and IR spectroscopy, mass spectrometry, elemental analysis and X‐ray crystallography. The compounds form asymmetric aggregates containing the novel Zn₄N₈ core; tetrahedra of Zn atoms bear the alkyl groups at Zn, with the triangular faces bridged by NHNMe₂ substituents. The NH groups are connected to two Zn atoms, and the NMe₂ groups to one. Hydrolysis of the compounds with water gives [(RZn)₄(OH)(NHNMe₂)₃] as products, which also were characterised as described above. Higher yields of these hydroxo clusters were achieved in one‐pot syntheses by reaction of dialkylzinc solutions with mixtures of N,N‐dimethylhydrazine and water. They contain Zn₄N₆O cages, in which one hydroxide in the tetrameric hydrazides described above replaces one NHNMe₂ group. Similar products can be prepared with alkoxy instead of hydroxy groups, in analogous one‐pot syntheses with alcohols. Alcoholysis of [EtZn(NHNMe₂)]₄ with methanol or ethanol gave zinc trishydrazide monoalkoxides, [(EtZn)₄(OR)(NHNMe₂)₃] (R = Me, Et), which have constitutions analogous to the monohydroxides. The organozinc bishydrazide bisalkoxides [(MeZn)₄(NHNMe₂)₂(OEt)₂] and [(EtZn)₄(NHNMe₂)₂(OEt)₂] were obtained in one‐pot reactions from dialkylzinc solutions with mixtures of the hydrazine and alcohol, and their crystal structures, confirmed by spectroscopic methods in solution, show an unsymmetrical aggregation with the novel Zn₄N₄O₂ cage structure.     

Synthesis and Crystal Structure of a Mixed－Valence Trinuclear Manganese Complex：Mn_3O（O_2CPh）_6（Py）_3

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆａＭｉｘｅｄ－ＶａｌｅｎｃｅＴｒｉｎｕｃｌｅａｒＭａｎｇａｎｅｓｅＣｏｍｐｌｅｘ：Ｍｎ_３Ｏ（Ｏ_２ＣＰｈ）_６（Ｐｙ）_３ＸｕＨａｏ；ＬｉＪｉｎ－Ｙｕ；ＬｉｕＱｉ；ＸｕＺｈｅｎｇ；ＹｏｕＸｉａ...     

High‐Pressure Synthesis and Single‐Crystal Structure Elucidation of the Indium Oxide‐Borate In4O2B2O7

The indium oxide‐borate In₄O₂B₂O₇ was synthesized under high‐pressure/high‐temperature conditions at 12.5 GPa/1420 K using a Walker‐type multianvil apparatus. Single‐crystal X‐ray structure elucidation showed edge‐sharing OIn₄ tetrahedra and B₂O₇ units building up the oxide‐borate. It crystallizes with Z = 8 in the monoclinic space group P2₁/n (no. 14) with a = 1016.54(3), b = 964.55(3), c = 1382.66(4) pm, and β = 109.7(1)°. The compound was also characterized by powder X‐ray diffraction and vibrational spectroscopy.     

3-叠氮-4-氨基呋咱的合成及其晶体结构

以乙二醛和盐酸羟胺为原料,经加成,闭环和氮化反应制备了新型含能化合物3-叠氮-4-氨基呋咱(AAF),其结构经NMR,IR,X-射线单晶衍射仪及元素分析表征。AAF晶体属单斜晶系,P21/c空间群,晶胞参数为:a=0.5329(16)nm,b=1.0722(3)nm,c=0.8492(2)nm,α=90.00°,β=99.03(2)°,γ=90.00°,V=0.5046(2)nm3,Dc=1.660g.cm-3,Z=4,F(000)=256,μ(MoKα)=0.138mm-1。最终偏离因子R1=0.0768,wR2=0.1983。AAF晶体存在分子间氢键。     

3-氨基-4-氨基肟基呋咱的合成及其晶体结构

以丙二腈为原料,用一锅法合成了呋咱类含能化合物3-氨基-4-氨基肟基呋咱(AAOF),收率72.4%。用1H NMR,13C NMR,IR,MS,元素分析和四圆单晶X-射线衍射仪对其分子和晶体结构进行了表征。结果表明:AAOF晶体属单斜晶系,空间群P21/c。主要晶体结构参数为:a=0.7651(3)nm,b=1.1702(3)nm,c=1.9216(10)nm,β=96.47(4)°,V=1.7095(12)nm3,Z=12,Dc=1.668 g.cm-3,F(000)=888。AAOF分子共面性较好,晶体中存在分子内和分子间氢键。