Synthesis and structure of a pure inorganic polyoxo-metalate-based porous framework

A pure inorganic porous framework based on the tungstoferrate[FeW₁₂O₄₀]^5-,Fe（H₂O）₆H[Na₆FeW₁₂O₄₀]₂·44H₂O（1） was obtained by the conventional aqueous solution method and characterized by elemental analysis,TG,FT-IR,UV-vis spectroscopy. Single-crystal X-ray diffraction analyses reveal that compound 1 crystallizes in the space group Fm-3m,which is composed of a porous inorganic framework[Na₆FeW₁₂O₄₀]_n with two kinds of pores A and B,accommodating Fe（H₂O）₆ units in pore A,which was observed rarely in the pure inorganic framework.     

Two Polynuclear Fe Complexes with Boat-like Core:Syntheses,Structures and Magnetic Properties

Two novel polynuclear complexes{NaFe4（μ₄-O）(L)4（μ₂-Cl）[Fe（CN）₅NO]（H₂O）(DMF)2}（1） and{NaFe4（μ₄-O）(L)4（μ₂-OEt）[Fe（CN）₅NO]（H₂O）(DMF)₂}（2） have been prepared using the tetradentate N-（2-hydroxyethyl）-3-methoxysalicylaldimine Schiff-base ligand （H₂L） with the help of[Fe（CN）₅NO]^2-linkers,where the ligand was in situ synthesized through the condensation of o-vanillin and e...     

Structural and Magnetic Characterization of Two New Coordination Compounds Based on a Fluorene Derivative Ligand

Two new coordination compounds[Co（FDC）₂（H₂O）₂]_n （1） and[Cu（FDC）₂（2,2?-bpy）]·DMF·H₂O（2）(HFDC=9-fluorenone-4-carboxylic acid,bpy=2,2?-bipyridine,DMF=N,N-dimethylformamide) were prepared by the reactions of corresponding metal salts with a fluorene derivative ligand of HFDC.Both compounds were thoroughly analyzed by X-ray single-crystal diffraction,elemental analysis,IR spectra,PXRDand thermal analysis.Compound 1 features a 1D struct...     

Luminescent Lanthanide-titanium-organic Compound Constructed by Tetra-nuclear Ln-Ti Building Units and Diphenylglycolic Acid

(Under solvothermal conditions with the mixed solvents of C₂H₅OH and H₂O,a new heterometallic lanthanide-titanium-organic compound,[TbTi(μ3-O)(L₃)(H₂O)₄]·H₃O(1,H₂L=diphenylglycolic acid),has been synthesized.Compound 1 exhibits a 3D supramolecular framework by incorporating the tetra-nuclear[Tb₂Ti₂(μ3-O)2]unit and L^2-ligand.Compound 1 shows intense green luminescence.Furthermore,the PXRD,TGA and IR spectra were also studied.)     

Noncentrosymmetric K2Mn3(SO4)3F2·4H2O and Rb2Mn3(SO4)3F2·2H2O with pseudo-KTP structures

Two fluoride sulfates,K₂Mn₃(SO₄)₃F₂·4H₂O(Ⅰ) and Rb₂Mn₃(SO₄)₃F₂·2H₂O (Ⅱ) are obtained by water solution method.Single-crystal X-ray diffraction analysis indicated that they crystallize in space groups of Cmc2_1.Their structures feature a pseudo-KTP structure consisting of interconnecting[Mn₃(SO₄)3F₂(H₂O)2]_∞ layers,which are further packing along the a axis with alkali metal cations balancing the charges.The structure relationships between the two compounds are discussed.Secondharmonic generation measurements manifest that Ⅰ and Ⅱ have similar second-harmonic generation responses of about 0.2 and 0.25 times that of KH₂PO₄.     

2,2′-二甲基-4,4′-联苯二甲酸构筑的两个金属有机骨架

以2,2′-二甲基-4,4′-联苯二甲酸(H2L)为配体,采用溶剂热法合成了2个金属有机骨架:[Ni(μ₂-H₂O)(L)(DMF)(H₂O)]·0.5H₂O(1)和[Cd_2.5(L)(trz)₃(H₂O)₂]·2.5DMF(2)(DMF=N,N-二甲基甲酰胺,Htrz=1,2,4-三氮唑)。借助红外、热重、粉末和单晶X射线衍射对其进行了表征。单晶结构分析表明,1结晶于单斜晶系的P2₁/c空间群,镍离子处在拉长的[NiO₆]八面体中且分别被μ₂-H₂O和L^2-配体连接形成二维sql拓扑网络。2结晶于单斜晶系,C2/m空间群,含有3个不同的镉离子且均为扭曲的八面体构型。3个镉离子被三氮唑负离子以μ_1,2,4-桥连,在ab平面形成二维的kgd层,这些层再被L^2-配体沿c轴支撑形成(4,8)双节点的三维flu拓扑网络。热重分析表明,1和2的网络分别在390和230℃发生分解。     

A unique organic-inorganic hybrid FeⅢ–PrⅢ-included 2-germano-20-tungstate and its electrochemical biosensing properties

An organic-inorganic hybrid Fe^Ⅲ–Pr^Ⅲ-included 2-germano-20-tungstate [Pr（H₂O）₈]₂H₂[Fe₄（H₂O）₄（pca）₄Ge₂W₂₀O₇₂]·34H₂O（Hpca=2-pyridinecarboxylic acid）(1) was hydrothermally prepared. Its polyoxoanion comprises one tetra-Fe^Ⅲ incorporated [Fe₄（H₂O）₄（pca）₄Ge₂W₂₀O₇₂]...     

以5-(6-羧酸-2-萘基)-间苯二羧酸为配体构筑的两个镉的金属-有机骨架化合物的合成、晶体结构及荧光性质

在溶剂热条件下,以不对称三羧酸5-（6-羧酸-2-萘基）-间苯二羧酸（H3L）为配体合成了2个镉的金属-有机骨架化合物:{[Cd₃L₂（H₂O）₃]·6DMF}_n（1）和{[Cd₃L₂（H₂O）₄]·3DMA}_n（2）。通过X射线单晶衍射,粉末衍射,热重和红外光谱进行了结构表征。结构分析表明,1和2形成3,6-连接的三维结构,其拓扑符号分别为:（4⁵.6⁴.8⁶）（4³）₂和(6¹².8³)（6³）₂。此外,还对2个化合物进行了荧光分析。     

A Robust Heterometallic Cd（Ⅱ）/Ba（Ⅱ）-Organic Framework with Exposed Amino Group and Active Sites Exhibiting Excellent CO2/CH4 and C2H2/CH4 Separation

A microporous and robust bimetal-organic framework [Cd₂Ba（NH₂-BTB）₂]·2（DMA）·2（H₂O）(1) was constructed by mixing the heterometallic nodes and an tridentate carboxyl ligand with amino group, benefiting from the synergistic effect of active sites, exposed amino groups and ultramicroporous structure. This compound displays an extraordinary selectivity of CO₂/CH₄ and C₂H₂/CH₄（16.7 and 146.3） at 298 K an...     

Syntheses and Structures of Two Coordination Polymers Containing Macrocyclic Oxamide and Isophthalic Acid Derivatives

Two novel coordination polymers [Cd(NiL)(aipt)](1) and [Mn(nipt)(NiL)₂]稨₂O(2)(NiL, H₂L=2,3-dioxo- 5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H₂aipt=5-aminoisophthalic acid, H₂nipt=5-nitroisoph- thalic acid) were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compounds 1 and 2 consist of different 1D chains including both oxamide and 5-aminoisophthalate or 5-nitroisophthalic bridge. And all these chains were further interlinked via hydrogen bonds, resulting in a 2D architecture in compounds 1 and 2.     

Synthesis,Crystal Structure and Fluorescent Properties of a 1D Europium Coordination Polymer with 2,5-Furandicarboxylic Acid

By using solvothermal method,a one-dimensional chain compound[KEu₂（FDCA）₃（H₂O）₉·0.5（FDCA）]（1） was synthesized.Single-crystal X-ray diffraction data reveal that 1 crystallizes in monoclinic system,space group P2₁/n with a=12.1996（1）,b=18.6454（2）,c=17.7123（2）?,β=98.8460（10）°,Dc=1.753 g/cm³,Z=2,V=3981.03（7）?³,R=0.0544 and wR=0.1511 for 7886 observed reflections with I>2σ（I）.In1,three FDCA^2– ligands construct ...     

Preparation and characterization of a novel single crystal of Th(IV) with cucurbit[6]uril

One new single crystal [Th(NO₃)₂(H₂O)₆](CB₆)(NO₃)2·2H₂O was prepared using Th(NO₃)4·4H₂O and cucurbit[6]uril (CB₆) as reagents in HNO₃ aqueous solution by slow evaporation. The coordination number of Th⁴⁺ is ten. Th⁴⁺ is coordinated with six monodentate water molecules and two symmetric bidentate chelating nitrate ions, while other two nitrate ions act as the counterion anions. CB₆ is a second-sphere ligand which is hydrogen bonded to the water molecules of [Th(NO₃)₂(H₂O)₆]²⁺. Besides, there are also two free water molecules in the crystal system.     

Two New Copper Complexes by H_4AQTC(Anthraquinone-1,4,5,8-tetracarboxylic Acid):Syntheses,Structures and Properties

Two new complexes[Cu(AQTC)_0.5(H₂O)₃]·3H₂O}_n (1,H₄AQTC=anthraquinone-1,4,5,8-tetracarboxylic acid) and Cu[(Py)₂C(OH)₂]₂(H₂AQTC)·2H₂O (2,(Py)₂CO=di-2-pyridyl ketone) have been prepared and characterized by elemental analyses and IR spectroscopy.X-ray crystallographic studies show that complex 1crystallizes in monoclinic space group C2/m and complex 2 in monoclinic space group P2_1/c.Complex 1 features a1D chain structure by carboxyl oxygen atoms.Complex 2 displays a mononuclear structure and anions and cations are separated.What's interesting is that the ligand of H₄AQTC with eight carboxyl oxygen atoms and two quinone oxygen atoms does not directly coordinate with metals,and only exist as a counter-anion in complex 2.Three-dimensional structures of two complexes are formed by intermolecular interactions.The thermogravimetric analyses of two complexes are investigated.The luminescent properties of complex 1 are investigated as well.     

基于席夫碱配体构筑的LnⅢ2配合物的结构、荧光性质及生物活性

以多齿席夫碱配体H₂L(H₂L=(E)-N′-(3-乙氧基-2-羟基亚苄基)-3-羟基吡啶甲酰肼)为配体,与Ln(acac)₃·2H₂O(Ln=Tb、Ho、Er;acac^-=乙酰丙酮根)反应,通过溶剂热法,成功得到了3例新的双核稀土配合物[Ln₂(acac)₂(L)₂(C₂H₅OH)₂](Ln=Tb((1)、Ho((2)、Er(3))。单晶X射线衍射分析表明：配合物1～3的结构主要由2个Ln^Ⅲ离子、2个乙酰丙酮根(acac^-)、2个L^2-及2个C₂H₅OH组成,中心Ln^Ⅲ离子通过2个μ₂-O原子相互连接,形成一个平行四边形的Ln₂O₂核心。固体荧光实验测...     

新型含氮配体钴配合物的水热合成、晶体结构及荧光性质

以4,5-二羟基苯-1,3-二磺酸钠（Na₂H₂L）和4,4′-bipy为原料,采用水热法与Co(NO₃)₂反应合成了新的含氮配体钴配合物[Co(4,4′-bipy)(H₂O)₄]·H₂L·2H₂O（1）（H₂L^2-=4,5-二羟基苯-1,3-二磺酸根离子,4,4′-bipy=4,4′-联吡啶）,其结构和组成经X-射线单晶衍射、红外光谱、元素分析和热重分析表征。晶体结构解析表明：钴离子与4,4′-bipy和水分子配位,形成扭曲的八面体配位构型。H₂L^2-配体没有配位,仅起平衡电荷作用。在结构单元中,[Co(4,4′-bipy)(H₂O)₄]²⁺, H₂L^2-和自由水分子之间通过氢键相连。配合物的荧光发射峰与配体相比发生了蓝移,最大发射峰位于357 nm。     

新型离子型配合物的合成、晶体结构及性质

利用水热法合成了4-(N,N′-双(4-羧基苄基)氨基)苯磺酸（H₃L）的两个离子型配合物：[Mn(phen)₂(H₂O)₂]?(HL)?(H₂O)₄（1）和[Zn(phen)₂(H₂O)₂]?(HL)?(H₂O)₆（2, phen =邻菲罗啉）,其结构经FL、 IR、元素分析、X-射线单晶衍射、 X-射线粉末衍射和TG表征。结果表明：化合物1属于单斜晶体,P2₁/c空间群,晶胞参数a=11.997(1) Å, b=22.978(1) Å, c=18.093(1) Å, β=92.749(3)°, V=4981.8(3) ų, Z=4。化合物2属于单斜晶体,P2₁/c空间群,晶胞参数a=11.861(1) Å, b=22.816(1) Å, c=18.251(1) Å, β=92.832(5)°, V=4932.8(5) ų,Z=4。化合物2有较好的荧光性质;初始分解温度为80 ℃。      

水合铵硼氧酸盐及其饱和溶液的FTIR和Raman光谱研究

研究了NH₄B₅O₈·4H₂O和(NH₄)₂B₈O₁₃·6H₂O及其饱和溶液于20℃的FTIR和Raman光谱,对振动频率进行了归属.根据振动光谱特征,预测(NH₄)₂B₈O₁₃·6H₂O中所含基本结构单元为[B₇O ₁₁(OH)·B(OH)₃]^2-.首次将Raman光谱中516cm^-1处的强散射峰归属为这一多聚硼氧配阴离子的对称脉冲振动峰,并对以上2种铵硼氧酸盐饱和溶液中硼氧配阴离子的存在形式{B(OH)₃,[B₃O₃(OH)₄]^-和[B₅O₆(OH)₄]^-}和相互作用机理进行了探讨.     

A Novel Co(Ⅱ)-organic Framework with Multiple Active Sites for Selective Gas Adsorption

A novel metal-organic framework[Co(BTTA)(H₂O)₂]_n(FJI-H₂4)has been prepared from H₂BTTA ligand and CoCl₂,and its structure was determined by single-crystal X-ray diffraction,thermogravimetric analysis,and Fourier transform infrared spectroscopy.It has relatively narrow pores and high density of open metal ions and free Lewis base sites.Gas adsorption tests demonstrate that FJI-H₂4 has moderate CO₂(34.0 cm³·g^–1)and C₂H₂(53.0 cm³·g^–1)adsorption capacity,but displays high selectivity of CO₂/N₂(87)and C₂H₂/CH₄(66)under ambient conditions(298 K,1 atm),which may be attributed to its relatively narrow pores and polar environment.This work will provide a potential strategy for preparing practical porous metal-organic frameworks for gas adsorption and purification.     

Two Alkali Metal Germanophosphates Na3[Ge(OH)(PO4)2]·2H2O and Li2Na[GeO(HPO4)(PO4)]:Crystal Structures and Thermal Stability

Two new alkali metal germanophosphates,namely,Na₃[Ge(OH)(PO₄)₂]·2 H2 O and Li₂Na[GeO(HPO₄)(PO₄)],have been prepared by solvothermal method,and their crystal structures were determined by single-crystal X-ray diffraction.The title two compounds crystalize in the same orthorhombic space group Pbcm(No.57)and feature similar chain-like structure which is built from zig-zag GeO₆ octahedral thread loop branched by PO₄ tetrahedra.For Na₃[Ge(OH)(PO₄)₂]·2 H₂O,a=10.1650(9),b=13.1975(12),c=6.9751(7)?,V=935.73(15)?³,Z=4,R=0.0356 and wR=0.1109;and for Li₂Na[GeO(HPO₄)(PO₄)],a=6.9855(5),b=14.5809(18),c=6.6620(5)?,V=678.56(11)?³,Z=4,R=0.0286,and w R=0.0762.The partial substitution of Na ions by Li ions not only significantly influences the total structural features and the water molecule contents,but also impacts on their thermal stabilities.Li₂Na[GeO(HPO₄)(PO₄)]is thermally stable up to 400℃,whereas only 150℃ for Na₃[Ge(OH)(PO₄)₂]·2 H2 O.     

基于2，5-二溴对苯二甲酸配体的锰/钴配合物的合成、晶体结构及性质

将有机物2,5-二溴对苯二甲酸(H₂L₁)作为主配体,2,2′-联吡啶(L₂)、1,10-菲咯啉(L₃)分别作为辅配体,通过溶剂热法与一水硫酸锰、六水合硝酸钴分别反应得到配合物[Mn₂(L₁)₂(L₂)₂(H₂O)₂]_n (1)和[Co₂(L₁)₂(L₃)₂(H₂O)₂]_n(2)。通过单晶X射线衍射法、荧光光谱、热重分析等测试手段对这2种配合物进行分析研究。结果表明配合物1是由Mn²⁺配位连接L₁^2-与L₂形成无限延伸的二维网络状结构,各层在分子间氢键和π-π堆积作用...