Syntheses, Crystal Structures and Thermal and Optical Properties of Two Organic Templated Gallium Antimony Sulfides

Two new gallium antimony sulfides,[enH2][Ga2Sb2S7]·en(1) and [puH]2[Ga2Sb2S7](2)(en = ethylenediamine,pu = propyleneurea),have been solvothermally synthesized.In the pre-paration of compound 2,the protonated propyleneurea cation as counterion and template was in situ synthesized by the reaction of 1,3-diaminopropane with CO2 in pyridine.Both structures contain a two-dimensional network composed of novel heterometallic clusters of {Ga2Sb2S9} as the second-dary building unit.The thermal and optical properties of compounds 1 and 2 were characterized by TGA and UV-Vis,respectively.     

过渡金属配合物为模板合成两个新的硫代锡酸盐(英)

利用溶剂热方法在温和的条件下合成了二个新的硫代锡酸盐[Mn(en)₃]₂Sn₂S₆·2H₂O(en=H₂NC₂H₄NH₂) (1)和[Mn(dien)₂]₂Sn₂S₆ (dien=H₂NC₂H₄NHC₂H₄NH₂) (2)，通过X-射线衍射分析表征其晶体结构。化合物1的晶体学参数：C₁₂H₄₈Mn₂N₁₂S₆Sn₂·2H₂O，M_r=936.28，单斜晶系，P2₁/c，a=1.012 9(3)，b=1.574 6(4)，c=1.152 4(3) nm，β=102.36(1)°，V=1.795 5(8) nm³，Z=2，D_c=1.732 g·cm^-3，μ(MoKα)=2.442 mm^-1，F(000)=940，R=0.063 3，wR=0.081 4；化合物2的晶体学参数：C₁₆H₅₂Mn₂N₁₂S₆Sn₂，M_r=952.32，单斜晶系，P2₁/c，a=1.248 12(3)，b=0.937 60(4), c=1.776 17 (7) nm，β=121.752(2)°，V=1.767 5(1) nm³，Z=2，D_c=1.789 g·cm^-3，μ(MoKα)=2.479 mm^-1，F(000)=956，R=0.057 9，wR=0.137 4。在两个化合物中存在的[Sn₂S₆]^4-阴离子均由共边的两个SnS₄四面体构成。在1中，锰离子螯合3个乙二胺做为阳离子模板，而在2中锰离子螯合2个二乙烯三胺做为阳离子模板。金属配合物作为模板对阴离子[Sn₂S₆]^4-在晶体结构中的排列产生重要的影响。     

A Strategy for the Preparation of Thioantimonates Based on the Concept of Weak Acids and Corresponding Strong Bases

By following a new synthetic approach, which is based on the in situ formation of a basic medium by the reaction between the strong base Sb(V)S₄^3? and the weak acid H₂O, it was possible to prepare three layered thioantimonate(III) compounds of composition [TM(2,2′‐bipyridine)₃][Sb₆S₁₀] (TM=Ni, Fe) and [Ni(4,4′‐dimethyl‐2,2′‐bipyridine)₃][Sb₆S₁₀] under hydrothermal conditions featuring two different thioantimonate(III) network topologies. The antimony source, Na₃SbS₄ ? 9 H₂O, undergoes several decomposition reactions and produces the Sb^IIIS₃ species, which condenses to generate the layered anion. The application of transition‐metal complexes avoids crystallization of dense phases. The reactions are very fast compared to conventional hydrothermal/solvothermal syntheses and are much less sensitive to changes of the reaction parameters.     

一种新的有机胺为模板剂的稀土硫酸钐合成，结构表征以及荧光性质

本文采用正丁醇与水的混合溶剂合成一种新的以有机胺为模板剂的硫酸钐盐:[C2N2H10]1.5[Sm(SO4)3(H2O)].2H2O(1),并通过X-射线衍射、红外、热重及元素分析对其进行了表征。该化合物晶体属于单斜晶系,P21/c空间群。其中a=0.65515(9)nm,b=2.648 3(4)nm,c=0.996 15(13)nm,β=104.067 0(10)°,V=1.676 5(4)nm3,Z=4。晶体结构分析显示化合物1中的波浪形层状结构由SmO9多面体与SO4多面体构成,同时非配位水与乙二胺通过氢键连接相邻的两个层。化合物1具有较强的荧光。     

四面体磷酸镓和磷酸锗镓构成的新型—维链状分子筛结构

以1，3-丙二胺为模板剂，在溶剂热条件下合成了两个一维磷酸盐微孔分子筛 ：[GaP2O7(OH)][NH3(CH2)3NH3](1)和[Ge0.5GaP1.5O6.5(OH)1.5][NH3(CH2)3NH3] (2).X射线单晶结构解析表明，两个晶体结构分别由镓氧四面体和磷氧四面体，或 镓氧四面体，锗氧四面体和磷氧四面体组成，并沿层c轴方向形成链，这些链之间 由1，3-丙二胺相连，1的结晶学数据为Mr=331.82,P-1,a=0.8303(2)nm,b=0.8614 (3)nm,c=0.8880(2)nm,a=111.70(3)°,β=107.5(92)°,γ=98.39(2)°，V=0. 5382(3)nm^3,Z=1,MoKa,λ=0.071073nm,R(F)=5.56,wR(F^2)=14.36,2的结晶学数据 为：P2（1）/c,a=0.88968(7)nm,b=1.67562(13)nm,c=0.83666(7)nm,β=115.890 (2),V=1.12208(16)nm^3,Z=4,MoKa,R(F)=4.66,wR(F2)=10.10。     

一种具有梯状链结构有机模板硫酸铽的合成、结构表征以及荧光性质

本文采用溶剂热法合成了一种具有梯状链结构新的有机模板硫酸铽盐:(C2H8N)[Tb(SO4)2.H2O](1),并通过X-射线衍射、红外、热重及元素分析对其进行了表征。该晶体属于单斜晶系,P21/n空间群。其中a=0.568 1(3)nm,b=1.972 7(10)nm,c=0.862 7(4)nm,β=90.658(6)°,V=0.966 7(8)nm3,Z=4。化合物1的骨架结构由TbO8多面体和SO4四面体构成。S(1)和S(2)与Tb(1)相连接,通过3个S-O-Tb连接构成双链,而相邻的双链通过μ3-O(O5)连接形成一个新的梯状链。     

以二亚乙基三胺为模板的链状结构硫酸钬配合物的合成、晶体结构及性质

通过溶剂热技术合成了一种以二亚乙基三胺(dien)为模板的链状结构硫酸钬(H₃dien)[Ho(SO₄)₃(H₂O)₂] (1),并通过X射线分析、红外光谱、元素分析和粉末衍射进行了表征。X射线晶体结构分析,化合物1结晶于单斜晶系,P2₁/c空间群,a=0.660 20(13) nm,b=1.476 7(3) nm,c=1.655 6(3)nm,β=93.313(2)°,V=1.611 4(5) nm³,Z=4。化合物1是由HoO₈多面体和SO₄四面体为建筑单元构建成新颖的单一链状结构。在a轴方向上,配位水分子通过氢键连接相邻的链形成三维超分子结构。有机胺分子镶嵌于链间,在合成化合物1合成过程中,pH值(pH=1.5)起了关键作用。     

Hydrothermal Synthesis, Crystal Structure and Luminescent Properties of an Organically Templated 2-D Uranyl Sulfate

An organically templated 2-D uranyl sulfate, {（C2H8N）[（UO2）Cl（SO4）（H2O）] }n 1, has been hydrothermally synthesized. The crystal and molecular structures have been determined by X-ray crystallography method and spectral techniques. 1 belongs to monoclinic, space group P21/c with a = 8.3545（17）, b = 10.550（2）, c = 12.370（3）A, β = 102.64（3）°, V = 1063.9（4）A3, Mr = 464.64, De= 2.901 g/cm^3, F（000） = 836,μ = 15.710 mm^-1, Z= 4, the final R = 0.0286 and wR = 0.0685 for 10164 observed reflections with Ⅰ 〉 2σ（Ⅰ）. 1 presents a two-dimensional layer-like structure constructed from infinite anionic [（UO2）Cl（H2O）（SO4）]^- layers with [C2H8N]^＋ cations balancing the charge and a number of intermoleeular hydrogen bonds （C-H…O and O-H…Cl） existing in the solid state. The fluorescence properties of 1 have also been discussed.     

Synthesis and Characterization of Two New Organically Templated Open-framework Uranium Phosphites

1 INTRODUCTION Uranium-based open-framework materials are the subject of significant investigation because of their relevance to radioactive waste management, ura- nium geochemistry and possible applications in ion exchange, catalysis, etc[1]. The crystal chemistry of hexavalent uranium is rich in structure style due to the high coordination numbers (six, seven, or eight) accessible to U6 and the polarized distribution of bond strengths within uranyl polyhedra. The area of metal phospho…     

A New One-dimensional Aluminium Fluorophosphate Templated by Organic Amine

A new one-dimensional aluminum fluorophosphate, AlP2O5(OH)3F·0.5[H2dien] (dien=diethylenetriamine), was solvothermally synthesized by using organic amine as the structure directing agent, and its structure was determined by single-crystal X-ray diffraction. The complex inorganic architecture consists of trans-corner-sharing AlO4F2 octahedra chain decorated by phosphate tetrahedra along both sides of the -F-Al-F-Al-F- backbone displaying a series of Al2P three-membered rings, which will represent a new fundamental structural type in metal phosphates. The results of CHN elemental analysis, EDS, and TGA are also presented. Crystal data: C4H18Al2F2N3O16P4, monoclinic, space group P21/c with a=6.9107(14), b=15.749(3), c=8.9741(18) , β=109.829(2)o, V=918.8(3) 3, Z=2, Mr=580.05, Dc=2.097 g/cm3, μ=0.618 mm-1, S=1.022, F(000)=590, the final R=0.0510 and wR=0.1284 for 1607 observed reflections (I > 2σ(I)).     

Syntheses,Characterizations, and Crystal Structures of Two New Organically Templated Borates

Two new organically templated borates, [H₂DAB][B₇O₉(OH)₅]·2H₂O ( 1 ) and [H₂DAB][B₇O₁₀(OH)₃] ( 2 ), have been synthesized under mild conditions in the presence of DAB acting as structure‐directing agent (DAB = 1,4‐diaminobutane). The structures were determined by single crystal X‐ray diffraction and further characterized by FTIR, elemental analysis, and thermogravimetric analysis. Both 1 and 2 crystallize in the same triclinic system, space group (No. 2); 1: a = 8.238(4) Å, b = 8.348 (5) Å, c = 14.574(8) Å, a = 101.050(3)°, β = 92.313(7)°, γ = 112.694(5)°, V = 900.3(8) ų, Z = 2; 2: a = 8.8769(3) Å, b = 9.3204(2) Å, c = 10.2204(5) Å, α = 74.474(2)°, β = 85.292(5)°, γ = 72.730(2)°, V = 778.01(5) ų, Z = 2. The structure of 1 consists of [B₇O₉(OH)₅]^2? groups, which represents the first example of organically templated heptaborate. The structure exhibits interesting hydrogen‐bonded network formed by borate polyanion [B₁₄O₂₀(OH)₆]^4?, which can be regarded as being constructed from the dehydration of the FBBs in 1 . The diprotonated organic amines are filled in the free space of the hydrogen‐bonded network and interact with the inorganic framework by extensive hydrogen bonds.     

Syntheses and Crystal Structures of Three Organically Templated Gallium Phosphates

Three open‐framework gallium phosphates [C₆H₁₆N₂][Ga(HPO₄)(PO₄)] ( 1 ), {H[C₆H₁₆N₂]₂[Ga₇(OH)₂(PO₄)₈]} ( 2 ), and {H[C₄H₁₂N₂]₂[Ga₇(OH)₂(PO₄)₈] · 2H₂O} ( 3 ) were solvothermally synthesized in the presence of 2,6‐dimethylpyrazine, N‐ethylpiperazine, and piperazine as templates, respectively. Compound 1 possesses an infinite one‐dimensional chain structure connected by hydrogen‐bond interactions to generate a 3D supramolecular framework. Compounds 2 and 3 show similar inorganic framework structures, which may be viewed as the assembly of a secondary building unit (SBU), Ga₆P₈ containing two GaO₄, two GaO₅, two GaO₆ as well as eight PO₄ groups. The SBUs are linked with each other by vertex‐sharing oxygen atoms to form 2D sheets, which are further connected by GaO₄ tetrahedra to result in the final 3D open‐framework with left‐ and right‐handed helical chains. In these materials, the well‐ordered organic species reside in the voids of structures and interact with the framework by way of hydrogen bonds.     

新型镍配合物的溶剂热合成及其晶体结构

以2-乙氧基-6-亚氨甲基苯酚(HL)为配体,与氨水和Ni(ClO4)2.6H2O经溶剂热法合成了新型镍配合物[Ni(L)2](1),其结构经IR,元素分析和XRD表征。1属三斜晶系,Pī空间群,晶胞参数a=0.843 3(3)nm,b=1.009 4(2)nm,c=1.188 4(2)nm,α=111.16(3)°,β=97.43(3)°,γ=102.43(3)°,V=0.897 2(11)nm3,Mr=387.05,Z=2,Dc=1 433 g.cm-3,F(000)=404,μ=1.105 mm-1,S=1.015。1中Ni2-分别与两个L-上的两个N原子和两个O原子配位,形成了平面四边形几何构型。分子通过一对N-H┈O氢键形成二聚体;二聚体进一步通过N-H┈O氢键和C-H┈Ni氢键的相互作用形成二维网状结构。     

Synthesis and Characterization of a New Organically Templated Aluminophosphite with a Chainlike Structure

A new aluminophosphite (H₄bape)_0.5[Al(OH)(HPO₃)₂] has been synthesized under hydrothermal conditions and its structure was determined by single‐crystal X‐ray diffraction (bape = N,N′‐bis(2‐aminopropyl)ethylenediamine). This compound crystallizes in the triclinic system with the space group (No. 2), a = 6.919(2) Å, b = 8.704(2) Å, c = 9.786(2) Å, α = 77.74(3)°, β = 72.43(3)°, γ = 72.52(3)°, V = 531.08(2) ų, Z = 2. The structure consists of distorted octahedral AlO₆ and pseudo pyramidal HPO₃, which are connected by vertex oxygen atoms to form a chainlike framework with a Al/P ratio of 1/2. The presence of 1D infinite Al‐O‐Al linkage in the framework is noteworthy. The organic templates are fully protonated and interact with the aluminophosphite chains through extensive hydrogen bonds to form a 3D supramolecular network.     

Selective synthesis of Fe7Se8 polyhedra with exposed high-index facets and Fe7Se8 nanorods by a solvothermal process in a binary solution and their collective intrinsic properties

Fe(7)Se(8) polyhedra with high-index facets and Fe(7)Se(8) nanorods can be selectively synthesized by a solvothermal reaction in a mixed solvent of diethylenetriamine (DETA) and deionized water (DIW). It is found that the morphologies of Fe(7)Se(8) nanocrystals can be effectively controlled by adjusting the volume ratio of DETA and DIW. The unusual polyhedral crystals are bounded by two {001} and twelve {012} facets. The intrinsic properties of Fe(7)Se(8) nanocrystals have been investigated. Magnetic measurements indicate that the obtained polyhedra and nanorods show a weak ferromagnetic ordering at room temperature. In particular, a new photoluminescence emission at 403 nm from the Fe(7)Se(8) nanocrystals has been observed. The described solvothermal reaction in a mixed solvent may be extended to the synthesis of other transition-metal chalcogenide crystals with controlled shape, facets, and structure, which may bring new functionalities.     

金属锑的同素异形体概述

结合最新研究进展,归纳总结了金属锑的同素异形体,包括块体锑(灰锑、爆炸性锑、黑锑、黄锑)和纳米锑(锑烯、锑纳米管).介绍了锑的各种同素异形体的组成、结构、性质、制备和应用等,为丰富金属元素的教学和扩展研究提供重要素材.     

茶多酚锗的合成及测试

茶多酚锗的合成及测试卢玉振＊张长庚（贵州大学化学系贵阳５５００２５）关键词茶多酚，茶多酚锗，合成，ＬＤ５０１９９６－０３－２６收稿，１９９６－０７－０２修回自从发现一些滋补性药用植物如人参、枸杞子等都含有微量锗以来，有机锗化合物的生化效应研究促进了有...     

The Rb7Bi3−3xSb3xCl16 Family: A Fully Inorganic Solid Solution with Room‐Temperature Luminescent Members

Low‐dimensional ns²‐metal halide compounds have received immense attention for applications in solid‐state lighting, optical thermometry and thermography, and scintillation. However, these are based primarily on the combination of organic cations with toxic Pb²⁺ or unstable Sn²⁺, and a stable inorganic luminescent material has yet to be found. Here, the zero‐dimensional Rb₇Sb₃Cl₁₆ phase, comprised of isolated [SbCl₆]^3? octahedra and edge‐sharing [Sb₂Cl₁₀]^4? dimers, shows room‐temperature photoluminescence (RT PL) centered at 560 nm with a quantum yield of 3.8±0.2 % at 296 K (99.4 % at 77 K). The temperature‐dependent PL lifetime rivals that of previous low‐dimensional materials with a specific temperature sensitivity above 0.06 K^?1 at RT, making it an excellent thermometric material. Utilizing both DFT and chemical substitution with Bi³⁺ in the Rb₇Bi_3?3xSb_3xCl₁₆ (x≤1) family, we present the edge‐shared [Sb₂Cl₁₀]^4? dimer as a design principle for Sb‐based luminescent materials.     

Novel Lanthanide (III) Complexes Derived from an Imidazole–Biphenyl–Carboxylate Ligand: Synthesis,Structure and Luminescence Properties

A series of neutral mononuclear lanthanide complexes [Ln(HL)₂(NO₃)₃] (Ln = La, Ce, Nd, Eu, Gd, Dy, Ho) with rigid bidentate ligand, HL (4′-(1H-imidazol-1-yl)biphenyl-4-carboxylic acid) were synthesized under solvothermal conditions. The coordination compounds have been characterized by infrared spectroscopy, thermogravimetry, powder X-ray diffraction and elemental analysis. According to X-ray diffraction, all the complexes are a series of isostructural compounds crystallized in the P2/n monoclinic space group. Additionally, solid-state luminescence measurements of all complexes show that [Eu(HL)₂(NO₃)₃] complex displays the characteristic emission peaks of Eu(III) ion at 593, 597, 615, and 651 nm.