Structural Characterization and Luminescence Properties of Two 4d-4fLn-Ag Coordination Compounds Based on Dinuclear Lanthanide Clusters

Two new compounds,[ErAg（INA）2（C2O4）]·2H2O（1）（HINA=nicotinic acid） and [Tb0.8Y0.2Ag2（IN）4·（H2O）5]·NO3·2H2O（2）（HIN=isonicotinic acid）,based on the {Ln2} building units,have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction,infrared spectroscopy,thermal analysis and powder X-ray diffraction（PXRD）.Single-crystal X-ray diffraction data reveal that both compounds crystallized in the low-symmetry triclinic space group P1-.Compound 1 is a 3D heterometallic coordination framework based on {Er2}clusters,oxalate ligands and bridging [Ag（INA）] linkers,while compound 2 consists of 0D [Tb0.8·Y0.2Ag2（IN）4（H2O）5]2 subunits that give a 3D supramolecular structure through hydrogen bond interaction.The photoluminescent properties of both compounds（1 and 2） were studied.     

两个多钒盖帽的Keggin型多铌钒酸盐衍生物的水热合成与表征

通过水热方法合成了2个由多铌酸盐和过渡金属配合物形成的有机-无机杂化配合物[Cu(TETA)]₄[VNb₁₂(VO)₄O₄₀][OH]·10H₂O(1)和[Cu(TETA)]₄[VNb₁₂(VO)₆O₄₀][OH]₅·5H₂O(2)(TETA=三亚乙基四胺). 化合物1和2的多阴离子分别是由4个{VO₅}帽和6个{VO₅}帽加盖在Keggin型多铌酸盐的方形缺口上形成的, 它们通过多酸阴离子中Nb-O_t (O_t =端氧)与[Cu(TETA)]²⁺配合物的金属中心配位构筑形成三维结构. 价键计算结果表明, Keggin中心的钒为+5价, 帽位的钒为+4价, X射线光电子能谱分析(XPS)结果也证实了这一结论. 通过单晶X射线衍射分析、红外光谱(IR)、粉末X射线衍射(PXRD)、热重(TG)分析和元素分析对这2个化合物的结构和性质进行了表征.     

Syntheses,Crystal Structures and Luminescent Properties of Three New Gallium Complexes Containing Pyridine-2,6-dicarboxylic Acid

Three new gallium complexes formulated as [Ga(PDA)₂][Ga(H₂O)(PDA)(phen)]·4H₂O(1), [Ga(PDA)₂]· (H₂IN)·2H₂O(2) and [Ga(OH)(PDA)(H₂O)]₂(3)(H₂PDA=pyridine-2,6-dicarboxylic acid; phen=1,10-phenanthroline; HIN=isonicotinic acid) have been synthesized under hydrothermal conditions. In the mixed-ligand system of complex 1, PDA^2? and phen are connected to the central Ga³⁺ cation as tri- and bi-dentate ligands, respectively. In complex 2, each Ga³⁺ cation is six-coordinated by two PDA^2? anions octahedrally. Complex 3 shows a binuclear structure, with the bond distance of Ga1-Ga2 being 0.30061(3) nm. The 3D supramolecular structures of the three complexes are constructed via hydrogen bonds and aromatic π-π packing interactions. All the three complexes exhibit intense blue emission at room temperature in the solid state, which are attributed to π^*-π transition centered on the ligands.     

Three Ni(Ⅱ) Coordination Polymers with Various Architectures Based on Asymmetric Bis-pyridyl-amide and Polycarboxylates: Syntheses,Structures and Properties

Three different dimensional Ni(Ⅱ) coordination polymers,[Ni(3-pna)(HIP)(H₂O)₃]·H₂O(1),[Ni(3-pna)· (1,3,5-HBTC)](2) and [Ni₂(H₂O)(3-pna)₂(1,4-CHDC)₂]₄(3)(3-pna=3-pyridylnicotinamide, H₂HIP=5-hydroxyisoph-thalic acid, 1,3,5-H₃BTC=1,3,5-benzenetricarboxylic acid, 1,4-H₂CHDC=1,4-cyclohexanedicarboxylic acid), were synthesized under hydrothermal conditions and characterized by means of infrared spectra(IR), thermal gravimetric (TG) analyses, powder X-ray diffraction(PXRD) and single-crystal X-ray diffraction. Complex 1 has a structure of 1D single-stranded chain, which is further stretched by hydrogen-bond interactions to form a 2D supramolecular sheet. Complex 2 shows a 2D network, which is stretched to 3D supramolecular frameworks through hydrogen-bond interactions. Complex 3 reveals a 3D skeleton with a (3,3,6,6)-connected {3·7²}{3²·4}{3³·4²·5·7³·8⁵·9}{3³·4⁵·5²·7²·8²·9} topology. The effects of different polycarboxylates on the ultimate architectures of the complexes 1-3 were discussed. Furthermore, the fluorescent and photocatalytic properties of the title complexes were also investigated.     

Synthesis,Structure and Properties of Two New Coordination Polymers Based on 4-[（8-Hydroxy-5-quinolinyl）azo]-benzenesulfonic Acid

Two new coordination polymers based on 4-[（8-hydroxy-5-quinolinyl）azo]-benzenesulfonic acid（H2L）,{[CdL（H2O）2]·H2O}n（1） and {[CdL（en）]·EtOH}n（2）（en=ethylenediamine）,were solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Compounds 1 and 2 exhibit infinite 1D ladder-shaped chain structures,which are isostructural except that the two coordinating water molecules in compound 1 were replaced by one en molecule in compound 2 due to the use of different organic base.Compounds 1 and 2 were constructed into different supramolecular frameworks by hydrogen bonding and π…π stacking interactions.In addition,the fluorescent properties of compounds 1 and 2 were investigated.Furthermore,they were also investigated via IR spectral analysis,elemental analysis,powder X-ray diffraction（PXRD） and thermogravimetric analysis（TGA）.     

Four Coordination Polymers Assembled with a New Biscarboxyl-functionalized Schiff Base Ligand

Based on a new biscarboxyl-functionalized Schiff base ligand 1,2-cyclohexanediamino-N,N'-bis[3-methoxyl-5-(p-carboxyl-phenylazo)] salicylidene(H₄L), four polymers,[(CH₃)₂NH₂]₂·[Mn₃(L)₂(H₂O)₄]·2DMF(CP1),[Fe₂(L)(H₂O)(DMF)](CP2),[(CH₃)₂NH₂]·[Cu(HL)]·H₂O(CP3) and[Ni₂(L)(teta)]·2DMF·H₂O(CP4), have been synthesized(teta=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). In CP1, both of the internal[N₂O₂] pocket and the external carboxylate groups of L^4- anion are ligated by Mn²⁺ ions, and the structure displays a layer. In CP2, the Fe²⁺ cations are linked by L^4- anions to form a binuclear double chain. CP3 displays a[Cu₂(HL)₂] dimer. In CP4, the Ni²⁺ ions are connected by L^4- anions to form a chain. The structures are further linked by hydrogen bonds to form 2D or 3D supramolecular architectures, respectively. CP1 exhibits adsorption ability to three organic dyes.     

Syntheses and structural characterization of trivalent lanthanide complexes of p-sulfonatothiacalix[4]arene

The X-ray crystallographic studies are reported for the water-soluble trivalent lanthanide complexes of the macrocyclic p-sulfonatothiacalix[4]arene [Gd(H₂O)₆((CH₃)₂SO)(p-sulfonatothiacalix[4]arene)]·H₃O⁺·5H₂O (1) and Na[Nd(H₂O)₆((CH₃)₂SO)(p-sulfonatothiacalix[4]arene)]·3H₂O (2). The complexes are isostructural and belong to monoclinic system, C2/m space group. The Ln³⁺ metal ion is coordinated by the thiacalixarene ligand via the sulfonato group, and also ligated by an oxygen atom of a dimethyl sulfoxide (DMSO) molecule that occupies the cavity of the thiacalixarene and six aqua ligands. The thiacalixarenes are linked by the coordinated water molecules through hydrogen bonding to form a 2D polymer. The p-sulfonatothiacalixarenes maintain the clay-like bi-layer structure in the coordination network.     

Mn(II)配合物的晶体结构及表面光电性能

采用水热法合成3个新的Mn(II)配合物[Mn(SO₄)(H₂O)₃]_n (1), [Mn2.5(HPO₄)(PO₄)(H₂O)₂]_n (2), [Mn(phen)₂(H₂O)₂]·(C₄H₄O₄)·4H₂O (3) (phen=1,10-邻二氮杂菲). 用X射线单晶衍射、表面光电压光谱(SPS)、红外光谱(IR)、紫外-可见吸收光谱(UV-Vis)、电子顺磁共振谱(EPR)对配合物进行了表征. 结构解析表明: 配合物1是具有2D结构的配合物, 氢键将其连接成3D超分子; 配合物2是具有3D无限结构的配合物; 配合物3是单核配合物, 再由多种氢键连接, 形成3D超分子. SPS结果表明, 3个配合物在300-800 nm范围内都呈现明显的光伏响应, 表明它们均具有一定的光-电转换性能. 讨论了配合物结构, 空间维度和中心金属离子配位环境的不同对配合物表面光电性能的影响以及SPS与UV-Vis的关联: 配合物的结构维度越高、规则性越好, SPS响应强度越大; 中心金属离子的直接配位原子种类的不同、所处外晶场的强弱不同, SPS响应带的数目和位置明显不同.     

邻菲啰啉和氨三乙酸钴配合物与牛血清白蛋白相互作用的荧光分析

利用溶液法合成了邻菲啰啉(phen)和氨三乙酸(H₃nta)钴配合物Co(phen)₂Cl₂(1), Na[Co(nta)]·H₂O(2), [Co(phen)₂(H₂O)₂][Co(nta)(phen)]₂·12H₂O(3), 对配合物3进行了X射线单晶衍射表征, 结果表明: 该配合物属三斜晶系, P1空间群, a=1.2448(2) nm, b=1.5898(3) nm, c=1.7412(3) nm, α=91.746(3)°, β=97.807(3)°, γ=103.745(3)°, V=3.309(1) nm³. 利用荧光光谱法研究了室温下这3种配合物与牛血清白蛋白(BSA)的相互作用, 并测定了不同温度下这3种配合物与BSA相互作用的荧光强度变化, 确定配合物1和3对BSA的荧光猝灭方式均为静态猝灭; 分析了配合物1和3与BSA相互作用时的结合常数、 结合位点数以及热力学函数与温度之间的关系, 进一步讨论了这2种配合物分别与BSA相互作用时的作用位点、 作用力的类型以及两者之间的距离.     

Hydrothermal Synthesis,Structure and Property of Transition Metal(Mn,Zn, Cd or Pb) Coordination Frameworks Using Quinoline-8-oxy-acetate Acid and Dicarboxylic Acid as Ligands

Five transition metal coordination compounds, [Mn₂(8-qoac)₂(bdc)(H₂O)₄](1)(8-qoacH=quinoline-8-oxy- acetate acid, H₂bdc=benzene-1,4-dicarboxylic acid), [Zn₄(8-qoac)₄(bdc)₂]_n(2), {[Cd₂(8-qoac)₂(Hip)₂(H₂O)₂]· (H₂O)₄}_n(3)(H₂ip=benzene-1,3-dicarboxylic acid), [Pb₃(8-qoac)₂(bdc)_1.5(H₂O)Cl]_n(4) and [Zn₂(8-qoac)(8-ql)(bdc)]_n (5)(8-Hql=8-hydroxyquinoline), were synthesized by hydrothermal syntheses of metal salts with benzenedicarboxy- lic acid and 8-qoacH. Compound 1 possesses a discrete dimer bridged by bdc^2- ligand. Compound 2 presents a 2D layer network constructed from bdc^2- linkers and 1D infinite ribbons, in which Zn(II) centers are bridged by 8-qoac^- with a tetradentate binding mode. Compound 3 displays a 1D zigzag chain, with adjacent chains further connected via extensive O-H···O hydrogen bonds to generate a 3D supramolecular structure. Compound 4 shows a 3D framework containing trinuclear lead secondary building units and bdc^2- linkers, in which a new coordination mode of 8-qoac^- ligand is observed. In compound 5, Zn(II) ions are simultaneously bridged by 8-qoac^-, 8-ql^- and bdc^2- ligands to form tetranuclear zinc units, which are further interlinked by bdc^2- linkers to yield a 2D wave-like layer. Based on intraligand(IL)(π-π^*) fluorescent emission, compounds 1―5 possess strong purple fluorescent emissions. In addition, the thermal stabilities of compounds 1―5 were studied.     

Crystal Engineering of Multiple-component Organic Compound:Organic co-Crystals of the Functional Groups of Carboxyl and Amino with Persistent Hydrogen Bonding Motifs

Three small organic molecular co-crystal compounds (C₃N₆H₆)·(C₆H₁₀O₄)·H₂O(1), C₃H₈N₂O(3) and (H₄btec)₂·(4,4'-bipy)(4)(H₄btec=1,2,4,5-benzenetetracarboxylic acid, 4,4'-bipy=4,4'-bipyridine) and one coordination supramolecular compound [Mn(C₂O₄)(H₂O)₂]·C₆H₁₁NO₂(2) were synthesized by hydrothermal reaction. They were characterized by elemental analysis, infrared(IR) spectroscopy and single crystal X-ray diffraction(XRD). Structural analyses reveal that these 2D or 3D supramolecular networks of the compounds were formed by C―H···O, N―H···O, N―H···N, O―H···O and O―H···N hydrogen bonds. Therein, the functional groups of ―COOH, ―NH₂ and ―OH play important roles in constructing supramolecular architectures.     

铜配合物修饰的Dawson型钨磷酸盐的合成、晶体结构和催化性能

在水热条件下,Cu(Ⅱ)-H₂biim配合物与Dawson型钨磷酸盐构筑了1个无机-有机杂化化合物[Cu(H₂biim)₂(H₂O)][{Cu(H₂biim)₂}₂(P₂W₁₈O₆₂)]·11H₂O(1)(H₂biim=2,2'-联咪唑)。 通过单晶X射线衍射、红外光谱(IR)、X射线粉末衍射(XRD)、元素分析、电化学分析等技术手段对其进行了表征。 结构分析表明,在化合物1分子中,[P₂W₁₈O₆₂]^6-单元作为双齿配体与2个Cu²⁺离子配位形成双支撑的杂多阴离子[{Cu(H₂biim)₂}₂(P₂W₁₈O₆₂)]^2-,在其外部有1个游离的[Cu(H₂biim)₂(H₂O)]²⁺ 和11个H₂O分子。 H₂biim分子与杂多阴离子/H₂O分子间存在氢键,通过氢键、静电和π-π堆积作用,进一步构成具有3D结构的晶体材料。 该晶体化合物对H₂O₂和NaNO₂的还原具有良好的电催化作用;同时,作为酸催化剂用于合成环己酮乙二醇缩酮反应,催化活性高,可重复使用。     

Molecular, supramolecular structure and catalytic activity of transition metal complexes of phenoxy acetic acid derivatives

Six mononuclear complexes [M(L₁)₂(H₂O)₄] (M = Co(II), 1a and M = Mn(II), 1b), [Cu(L₁)₂(H₂O)₂] (1c), [Cu(L₁)₂(H₂O)(Py)₂] (1d), [Cu(L₃)(H₂O)Cl] · H₂O (3a) and [Co(Sal)(H₂O)(Py)₃] · 2ClO₄ · H₂O (3b) of phenoxyacetic acid derivatives and Schiff base were determined by single crystal X-ray diffraction. The Co(II) (1a) and Mn(II) (1b) complexes are isomorphous. X-ray crystal structural analyses reveal that these coordination complexes form polymeric structure via formation of different types of hydrogen bonding and π-stacking interactions in solid. Thermal analysis along with the powder X-ray diffraction data of these complexes shows the importance of the coordinated and/or crystal water molecules in stabilizing the MOF structure. Complexes 1a, 1c, 3a show marginal catalytic activity in the oxidation of olefins to epoxides in the presence of i-butyraldehyde and molecular oxygen.     

Carboxylate-induced Various Structures of Ni(II) Complexes with Fluorescence Sensing and Bifunctional Electrochemical Properties

We synthesized three new Ni(II) coordination polymers [Ni(LXHLPXH2O)2]- H2O(CP1),[Ni(LXNIP)]-2H2O(CP2) and [Ni(LXNDCXH20)2](CP3)[L=N,N′-bis(pyridme-3-yl)thiophene-2,5-dicarboxamide, H2HIP=5-hydroxyisophthalic acid, H2NIP=5-nitroisophthalic acid, H2NDC=2,6-naphthalenedicarboxylie acid] by hydrothermal method, which were characterized by means of infrared spectra(IR), TG analyses, PXRD and single-crystal X-ray diffraction. The CPI is a ID tubular structure based on [Ni-HIP]2 loops and pairs of L ligands. CP2 is a 2D 3,5-connected architecture, which consists of Ni-L linear chains and (Ni-NIP)2 double chains. CP3 is a 2D network, which features 4-connected topology. Solid-state luminescent behaviours of CP-P3 were investigated. The CPI can detect Fe^3+ ions through luminescence quenching. The electrochemical properties of CPI buk-modified carbon paste electrode(CP1-CPE) has also been investigated, which has bifunctional electrocatalytic activity for oxidation of ascorbic acid and reduction of NO2^-.     

Hydrothermal Syntheses and Characterization of Two 1D Chain Complexes and Tetra-capped Keggin Clusters

Two new compounds, [Ni(en)₂]{[Ni(en)₂]₂[Mo^VI₆Mo^V₂V^IV₈O₄₀(SiO₄)]}[(NH₂)₂(C₂H₄)₂NH]·2H₂O(1) and [Ni(en)₂]{[Ni(en)₂]₂[Mo^VI₅Mo^V₃V^IV₈O₄₀(VO₄)]}(en)·H₂O(2)(en=ethylenediamine), have been hydrothermally synthesized and characterized by elemental analysis, infrared(IR), X-ray photoelectron spectroscopy(XPS), electron spin-resonance(ESR) and thermogravimetric(TG) analysis and single-crystal X-ray diffraction(XRD) analysis. Both the compounds exhibit a 1D chain composed of bi-supporting tetra-capped Keggin clusters and nickle coordination fragments. The 1D chains are further assembled into a 3D supramolecular network with different packing modes via hydrogen bonds. The magnetic susceptibility of compound 1 demonstrates the presence of antiferromagnetic interactions.     

系列Cu(Ⅱ/Ⅰ)配聚物的合成、结构及光电性能

采用水热方法合成了3种Cu(Ⅱ/Ⅰ)配聚物及超分子, (1) [K₂Cu₂(ox)(btec)(MeOH)₂]_n, (2) {[Cu(pdc)(H₂O)₂]?H₂O}_n, (3) [Cu(cyan)(phen)]?H₂O (H₂ox: 草酸, H₄btec: 均苯四甲酸, MeOH: 甲醇, H₂pdc: 2, 5-吡啶二羧酸, phen: 邻菲啰啉, Hcyan: 氰尿酸). 通过X射线单晶衍射、表面光电压光谱(SPS)、固体紫外-可见(UV-Vis)、傅里叶变换红外(FTIR)光谱、元素分析等方法对配合物进行了表征. 结构解析结果表明, 配合物(1)是具有三维(3D)无限结构的配聚物; (2)是具有二维(2D)无限结构的配聚物, 但又通过氢键进一步连成了三维(3D)网络, (1)与(2)的中心金属均为Cu(II)离子; (3)为含Cu(I)的单核配合物, 但又通过氢键和π-π堆积作用, 使它成为2D超分子化合物. 配合物SPS结果显示, 配合物(1)-(3)在300-800 nm范围内都呈现光伏响应, 表明三者均具有一定的光电转换能力. 讨论了配合物的组成、结构、维数、配体种类、中心金属离子价态及配位微环境对SPS的影响,并将SPS与UV-Vis 光谱进行了关联.     

New Tetraazamacrocyclic Ligand with Neutral Pendent Groups 1,4,7,10-tetrakis (2-cyanoethyl)-l,4,7,10-tetraazacyclododecane (L) and Its Cobalt (Ⅱ), Nickel (Ⅱ) and Copper (Ⅱ) Complexes:Synthesis,Structural Characterization and Antitumor Activities

A new tetraazamacrocyclic ligand (L) with four neutral 2-cyanoethyl pendent groups and its divalent transition-metal complexes:[Co(L)(NO₃)]NO₃·H₂O (1),[Ni(L)(NO₃)]NO₃·3H₂O (2) and[Cu(L)(H₂O)](NO₃)₂ (3) have been synthesized. The crystal structures of (1) and (3) have been determined by X-ray analysis. In complex (1) the cobalt atom is coordinated by four nitrogen atoms and two oxygen atoms of a nitrate anion, which define a distorted octahedron. The other nitrate ion lies in the lattice as a counter ion.     

三维化合物[Ni2(BDC)2(m-bix)(H2O)3·3H2O]n的合成、结构和性质

水热条件下,合成了一个三维配位聚合物[Ni₂(BDC)₂(m-bix)(H₂O)₃·3H₂O]_n(1)[BDC=对苯二甲酸,m-bix=1,3-双(咪唑基-1-甲基)-苯],并通过红外,热重和X-射线单晶衍射进行了表征。X射线衍射结果表明化合物含有类似配位环境的金属2个Ni²⁺离子,2个BDC^2-配体,1个m-bix分子,3个配位水分子和3个游离的溶剂水分子。两个Ni²⁺离子分别采用八面体构型,通过桥联水分子形成双核单元,然后通过全部脱质子的BDC形成三维孔洞结构,m-bix配体通过连接两类双核金属原子形成三维框架,游离水分子存在于框架之中。有趣的是,化合物的结构是单一六节点,具有自穿插特征。而且对化合物的红外和热重性质进行了表征。     

Crystal structure and luminescence property of ternary terbium p-aminobenzoic acid complexes with different second ligands

Ternary terbium complexes with p-aminobenzoic acid (HL), [TbL₃(DMSO)(H₂O)]₂ (1), [TbL₃(DMF)(H₂O)]₂ (2) and [TbL₃(Bpy)(H₂O)]₂·2H₂O (3) (DMSO=dimethyl sulfoxide, DMF=N, N- dimethylformamide, Bpy=2, 2′- bipyridyl) have been synthesized, and their crystal structures determined. The luminescence properties of these complexes, including both the emission quantum yield and the fluorescence lifetime, have been investigated. The effect of a second ligand on the crystal structure and luminescence property of the ternary terbium p-aminobenzoic acid complexes, and the relationship between luminescence properties and crystal structure, including coordination mode of the L⁻ ligand and the characteristics of a second ligand, are discussed.     

Cd(Ⅱ)-btec配聚物的合成、结构及光电性能

采用水热法合成了Cd(Ⅱ)配聚物[Cd₃Na₂(btec)_n(1)和{[Cd₃Na₂(btec)₂(H₂O)₂]·4H₂O}_n(2)(H₄btec=1,2,4,5-苯四甲酸). 单晶结构解析结果表明, 配聚物1和2的不对称单元中均包含2种晶体学不等效的Cd(Ⅱ)离子, 分别为六配位和八配位, 均通过btec^4-基团桥连成具有3D无限结构的配聚物. 二者区别在于: 2个配聚物中Na(Ⅰ)离子的配位环境不同, 且配聚物2中存在游离水分子. 表面光伏技术研究结果表明, 2个配聚物在300~500 nm范围内呈现出明显的光伏响应, 表明它们具有一定的光-电转换能力. 对配聚物的表面光电压谱(SPS)与紫外-可见吸收光谱(UV-Vis)进行了关联, 并对配聚物进行了X射线衍射(XRD)和热重(TG)分析.