A Novel 3D CdⅡ-CP Based on a Bi-functional（N-/O-Sites） Triazole-modified Carboxyl Ligand: Structure,Topology and Photoluminescence

With triazole-modified derivative as link,one new framework[Cd₅(μ₅-HL^2-)₂(μ₄-L^3-)₂（H₂O）₁₀]·2H₂O(1,H₃L=2-（1,2,4-triazol-1-yl）benzene-1,3,5-tricarboxylic acid) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction,powder X-ray diffraction and elemental analysis.Complex 1exhibits a 3D （3,4,6）-connected net cross-linked by binuclear[Cd₂     

One Novel Ag(Ⅰ) Compound Generated from Double Schiff-base Ligand with Quinoxaline-N-oxide as Terminal Binding Sites

One novel discrete coordination molecule with Ag^I centers,namely[Ag₃(L)₃(ClO₄)₃]·3CH₂Cl₂·6CH₃OH·1.5H₂O (1),has been synthesized based on the double Schiff-base ligand,3,6-bis[2-(4-oxidequinoxaline)-yl]-4,5-diaza-3,5-octadiene (L) and AgClO_4.The obtained Ag(I) compound was fully characterized by infrared spectroscopy,elemental analysis,and single-crystal X-ray diffraction.1 is of trigonal system space group P-31c with a=16.320(2),b=16.320(2),c=20.108(6)?,T=173(2) K,V=4638.2(16) A³,D_c=1.645 g/cm³,M_r=2297.33,Z=2,F(000)=2334,μ=0.970 mm~(–1),Goodness-of-fit=1.109,the final R=0.0776,wR=0.1813,Rindices (all data)=0.1196,wR=0.2011.The compound exhibits a triple-helical[Ag₃L₃]³⁺crown-like trimer,in which three Ag(I) atoms form an equilateral triangle with the Ag···Ag distance of 4.7 A.Uncoordinated counterions ClO₄^– and solvent molecules methanol generate the hydrogen-bonded frameworks based on discrete molecular complex building blocks.     

Detection of Diethyl Ether by a Europium MOF through Fluorescence Enhancement

A new water-stable europium MOF,(Me₂NH₂)[Eu(abtc)(phen)]·2H₂O (1),has been synthesized from Eu(NO₃)₃·6H₂O with 1,10-phenanthroline (phen) and 3,3′,5,5′-azobenzenetetracarboxylic acid (H_4abtc) ligands under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction analysis,IR,TGA and PXRD.It crystallizes in monoclinic system,C2/c space group,with a=16.278(3),b=14.261(3),c=27.936(5)?,b=103.464(3)°,V=6307(2)A³,Z=8,C₃₀H₂₆Eu N_5O₁₀,M_r=768.5,D_c=1.543 g/cm³,F(000)=2912,m(Mo Ka)=2.044 mm^-1,R=0.0315 and w R=0.0663.In the structure of 1,the Eu O_7N₂ polyhedra are assembled into a 2D layer with rhombic windows and these layers are further condensed to form a 3D framework.It can be used as selective and sensitive fluorescence sensors capable of detecting diethyl ether vapor.     

Hydrothermal Synthesis,Crystal Structure and Properties of a New Binuclear Nickel(Ⅲ) Complex with 3-(Pyridin-2-yl)-1,2,4-triazole

A new binuclear nickel(II) complex Ni₂(HPT)_4(H₂O)₃ (1) has been hydrothermally synthesized with nickel hydroxide,3,4-pyridine dicarboxylic acid and 3-(pyridin-2-yl)-1,2,4-triazole (HPT) in the mixed solution (the volume ratio of methanol and water is 1:4).It crystallizes in tetragonal space group P4₂/n,with a=20.844(1),b=20.844(1),c=7.2463(7)A,V=3148.2(5)A³,D_c=1.587 g/cm³,Z=4,μ(Mo Ka)=1.257,F(000)=1544,the final GOOF=1.043,R=0.0437 and w R=0.1297.The crystal structure shows that the whole molecule consists of two nickel ions which are bridged by fourμ₂-η¹:η^0-3-(pyridin-2-yl)-1,2,4-triazole anions.The coordination environment of Ni(II) ion is Ni N₆,giving a distorted octahedral geometry.The thermal stability and fluorescent and magnetic properties of the complex were investigated.     

系列Sm3+配合物的合成、结构及光物理性能

采用水热方法合成了4种Sm³⁺配合物, 即{[SmZn(2,5-pdc)₂(tp)_0.5(H₂O)]·2H₂O}_n(1), [Sm₂Zn₂(C₆H₅COO)₁₀(Imh)₂(H₂O)₂](2), {[Sm₂(NO₂C₆H₄COO)₆(H₂O)₄]·H₂O}_n(3)和{[SmN(CH₂COO)₃(H₂O)₂]·H₂O}_n(4)[2,5-pdc=2,5-吡啶二羧酸根, tp=对苯二甲酸根, C₆H₅COO=苯甲酸根, Imh=咪唑, NO₂C₆H₄COO=对硝基苯甲酸根, N(CH₂COO)₃=氨三乙酸根]. 通过单晶X射线衍射确定了其晶体结构. 在室温下测定了其红外光谱、 紫外-可见-近红外光谱以及在近红外区和可见区的发射光谱. 结果表明, 4种配合物在近红外区或可见区均出现Sm³⁺离子的特征发射. 这是形成配合物后, Zn-配体部分和配体对Sm³⁺离子发光的敏化作用所致. 此外, 讨论了不同有机配体或d过渡金属离子对Sm³⁺离子发光的影响, 并分析了配合物中Sm³⁺离子的近红外发射带位移、 劈裂和加宽的原因.     

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.     

Two isostructural Ni(Ⅱ)/Co(Ⅱ)-based metal-organic frameworks for selective dye adsorption and catalytic cycloaddition of CO2 with epoxides

Two isostructu ral Ni(Ⅱ)/Co(Ⅱ)-based metal-organic frameworks(MOFs),namely {[M₃(L)₂(bpb)₃(H₂ O)₄]·2 DMF·2 H₂O}_n [M=Ni(HL-5,HL is short for Hui-Ling Liu);M=Co(HL-6);H₃ L=2',6'-dimethyl-[1,1'-biphenyl]-3,4',5-tricarboxylic acid;bpb=1,4-bis(pyrid-4-yl)benzene],have been hydrothermally synthesized and structu rally characterized.Both HL-5 and HL-6,which have the same three-interpenetrated3 D pillared-layer framework with sqc306 type topology,present good selective methyl orange(MO)adsorption over rhodamine B(RhB).Moreover,the catalytic CO₂ cycloaddition properties with epoxides of the two MOFs have also been studied at ambient pressure and temperature.     

4-(4-羧基苯氧基)间苯二甲酸构筑的过渡金属配位聚合物:合成、晶体结构、荧光传感与光催化

采用水热法合成了4个配位聚合物[Zn(Hcpoia)(2,2’-bpy)·H₂O]_n(1)和[M(Hcpoia)(phen)]_n·nH₂O[M=Zn(2),Mn(3),Co(4); H₃cpoia=4-(4-羧基苯氧基)间苯二甲酸; 2,2’-bpy=2,2’-联吡啶; phen=1,10-邻菲罗啉],利用X射线单晶衍射分析确定了配合物的晶体结构。配合物1为一维链状结构,中心Zn²⁺离子的配位环境为[ZnO₄N₂]扭曲的八面体构型,配体Hcpoia^2-以μ₁∶η¹η⁰和μ₁∶η¹η¹配位模式桥连相邻的Zn²⁺离子。配合物2和4的结构与配合物1类似,是由配体Hcpoia^2-以μ₁∶η¹     

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.     

Synthesis,Crystal Structure and Fluorescence Property of a Zinc(Ⅱ) Coordination Polymer with a Theoretical Calculatio

We have designed and synthesized a new luminescent coordination polymer[Zn₂(NO₃)(NCP)₃(H2O)₃]n·2 nH₂O(1,HNCP=2-(2-carboxyphenyl)imidazo-[4,5-f]-1,10-phenanthroline)under hydrothermal conditions,which has been structurally characterized by single-crystal X-ray diffraction analyses.1 crystallizes in monoclinic,space group P2₁/n,with a=13.7748(3),b=19.2651(4),c=19.9543(4)?,β=95.339(2)o,V=5272.35(19)?³,C₆₀ H_39.73 N₁₃ O_13.33 Zn₂,M_r=1286.80,D_c=1.621 g/cm³,Z=4,μ(Mo Ka)=2.118,F(000)=2629,the final R=0.0598 and w R=0.1483.In 1,the organic ligand NCP-displays two different bridging modes to connect adjacent Zn(II)ions into a 1 D chain along the c-direction.Photoluminescent analyses reveal that 1 exhibits a strong green emission with a fluorescent lifetime of 5.57 ns.The first-principle calculation results show that the luminescence mainly originates from ligand-centered charge transition.     

Synthesis,Crystal Structure and Antitumor Activity of a Ca(Ⅱ) Coordination Polymer Based on 4-Acetylphenoxyacetate Ligands

A novel Ca(Ⅱ) coordination polymer,[Ca L₂(H₂O)₂]_n (1,HL=4-acetylphenoxyacetic acid) has been synthesized with 4-acetylphenoxyacetic acid,Ca(ClO_4)₂·4H₂O and Na OH as raw materials.Complex 1 was characterized by elemental analysis and single-crystal X-ray diffraction analysis.The results show that the Ca(Ⅱ)ion is eight-coordinated in a distorted triangular dodecahedral geometric configuration with six carboxylate Oatoms of four L ligands and two O atoms of two coordinated water molecules.Complex 1 forms a one-dimensional chained structure by the bridging effect of carboxylate O atoms.The antitumor activity of HLligand and complex 1 has also been investigated.     

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 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.     

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 ℃。      

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...     

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]...     

Two Novel {Ti_6P_2} Clusters Decorated with Inorganic Acids

Two inorganic acids decorating titanium-oxo clusters (PTCs),Ti_6O_4(O~iPr)₁₀(O₃P-Phen)₂(NO₃)₂(PTC-251) and Ti_6O_4(O~iPr)₁₀(O₃P-Phen)₂(HSO_4)₂ (PTC-252)(H₂O₃P-Phen=phenylphosphinic acid) have been synthesized under solvothermal conditions.As a result of the labile coordination sites of the{Ti_6P₂}unit,nitrite and sulfate adopt different capping mode.Besides,they also present different space packing.The photocatalytic H₂evolution activities of these obtained PTCs have been studied,with sulfate decorating PTC-252 presenting a maximum H₂ production rate up to 110.95μmol·g^-1·h^-1.     

高氯酸二甘氨酸十二水合二铒的晶体结构

在水溶液中合成了甘氨酸铒配合物[Er₂(Gly)₂(H₂O)₁₂](ClO₄)₆·4H₂O单晶,并测定了其晶体结构。该晶体属单斜晶系,P2₁/n空间群。晶胞参数:a=1.0571(2)nm,b=1.0837(2)nm,c=1.7728(4)nm,β=90.09(3)°,V=2.0309(7)nm²,Z=2,D_c=2.239g/cm³.最终偏差因子R=0.055,R_w=0.061.每2个Er³⁺离子由2个甘氨酸羧基桥联成双核结构。Er³⁺离子还与6个水分子的氢原子配位,形成畸变的四方棱柱型配位多面体。     

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.     

磷酸铁锂废料中FePO4·2H2O提取及其杂质形成机理

采用化学共沉淀方法从磷酸铁锂废料中提取FePO₄·2H₂O,并研究了回收过程中杂质形成的机理。在热力学计算基础上绘制了298和363 K时Fe-P-Li-H₂O体系的电势(φ)-pH图,结果表明当pH≤5.0时,Fe(OH)₃相可以自发地转成FePO₄·2H₂O相,从而得到高纯的FePO₄·2H₂O。但实验结果发现当溶液中铁、磷的物质的量之比(n_Fe∶n_P)为1∶1,合成pH为1.5～2.2时得到的FePO₄·2H₂O中存在Fe(OH)₃杂质,这是因为在共沉淀过程中少量Fe³⁺以Fe(OH)₃快速沉淀,而陈化时Fe(OH)₃相转化速率慢,因此FePO₄·2H₂O中含有Fe(OH)₃