Template-directed Synthesis of Three Metal Oxalates via 4-Connected Building Units

Three novel compounds, [Co（en）3]2[Zr2（C2O4）7]·2H20（HNU-2, en=ethylenediamine）, [Co（NH3）6]· [Ce（CzO4）3（H2O）]·H2O（HNU-3） and [Co（dien）2][Gd（C2On）3]·0.75H2O（HNU-4, dien=dethylenetriamine） were hydro- thermal synthesized based on the templates of [Co（en）3]C13, [C0（NH3）6]C13 and [Co（dien）2]C13, respectively. The Zr4＋ Ce3＋ and Gd3＋ cations are all coordinated by four oxalates to form [M（C2O4）n（H2O）n]m （M=Zr, Ce or Gd; n=0 or 1; m=4 or 5）, which are similar to [In（C2O4）4]5- in NKB-1, and can be regarded as 4-connected building units. The [M（C2O4）a（H2O）n]m units are connected via sharing the bis-bidentate bridging oxalate ligands to form binuclears in HNU-2 and 1D ＂zigzag＂ chains in HNU-3 and HNU-4. cular building units to design 3D open frameworks with It is suggested that these compounds could be used as mole- zeolite topologies.     

One-dimensional infinite chain crown ether complex:Synthesis and crystal structure of[Na(18C6)]2[Cu(mnt)2]·H2O

One-dimensional coordination polymers have attracted considerable interest in recent years because of the prospect of electrical, optical and magnetic properties. Crown ether can form one-dimensional infinite chain structure with transition metal complex. We synthesized the complexes of 18-crown-6 with Na₂[m{S₂C₂(CN)₂}₂](m=Cu, Ni, Pd, Pt; S₂C₂(CN)₂^2- mnt) and now report the structure of complex[Na(18C6)]₂[Cu(mnt)₂]·H₂O.     

Synthesis and resonance raman study of conductive iodinated materials derived from [M(dmit)(phen)] complexes [M = Pd(II), Pt(II)]

The synthesis and characterization of the [M(dmit)(phen)] complexes [M = Pd(II), Pt(II); H₂dmit = 4,5-dimercapto-1,3-dithiole-2-thione; PHEN = 1,10-phenanthroline) and of the iodinated [M(dmit)(phen)]I compounds are described. The conductivity of [M(admit)(phen)] increases upon oxidation by a factor of 10⁶, and is ca. 5 × 10⁻³ ohm⁻ cm⁻ for the [M(admit)(phen)]I compounds. The nature of the iodine species in these solids is determined by UV-visible and resonance Raman spectroscopies. The only polyiodide present is I⁻₃ and, thus, the charge distribution can be expressed as [M(dmit) (phen)^0.33+[I⁻₃]_0.33.     

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-(1H-1,2,4-三唑-1-亚甲基)苯甲酸过渡金属配合物的合成、结构、抑菌活性及DNA裂解活性

Three novel transitionmetal compounds [Cu_0.5L]_n (1), {[Ni(L)₂·(H₂O)₂]·(H₂O)₂}_n(2), and {[Co(L)₂·(H₂O)₂]· (H₂O)₂}_n (3), were hydrothermally synthesized with 4-(1H-1,2,4-triazol-1-ylmethyl) benzoic acid (HL) and characterized by infrared spectroscopy, elemental analyses, single-crystal X-ray diffraction, thermal analyses, UV-Vis spectroscopy, and fluorescence spectroscopy. Structural analyses reveal that compound 1 features a one-dimensional (1D) chain, while isomorphic 2 and 3 exhibit a three-dimensional (3D) network structure with interchain hydrogen-bonding. Antifungal activities tests reveal that 1 has the highest antifungal effect on the five fungi (Fusarium graminearum, Vasa mali, Macrophoma kawatsukai, Colletotrichum gloeosporioides, and Alternaria alternate) among the three compounds. Furthermore, DNA cleavage experiments indicate that compound 1 has more efficient DNA (pUC 18) cleavage activity than compounds 2 and 3. The binding properties of the three compounds with DNA were also investigated by absorption. The results show that the three compounds can intercalate into DNA, and the interaction of compound 1 is the strongest.     

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.     

Third-order Optical Nonlinearities of a Series of Compounds Derived from a Keplerate Type Molybdenum-oxide-based Polyoxometalate

Abstract By reacting the unique Keplerate type molybdenum-oxide based polyoxometalate （NH4）42·[MoI320372·（CH3COO）30（H2O）y2]·ca.300H2·ca. 10CH3COONH4（1） with tetramethylammonium bromide, a new derivative （NH4）26[TMA]16{MoI32O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca.189H2O（2, TMA=tetramethylammonium） was prepared. Compound 2 was characterized by Fourier transform infrared spectroscopy（FTIR）, UV-Vis, elemental and thermogravimetric analyses. By the well-established Z-scan technique, investigations on the nonlinear opti- cal（NLO） properties of the series of compounds derived from the Keplerate type molybdenum-oxide-based poly- oxometalate, namely, the newly prepared compound 2, the three previously reported compounds, included compound 1, （NH4hs（TBA）24{Mo132O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca. 173H2O（3, TBA=tetrabutylammonium） and （DODA）40（NH4）2[（H2O）nMo132O372（CH3COO）3o（H20）72]（4, DODA=dimethyldioctadecylammonium）, reveal that the third-order nonlinearity[x（3）] values of compounds 1, 2 and 3 in the DMF/H2O solution and compound 4 in chloro- form are almost the same, which indicates that the counter cations with different length of alkyl chains show ignora- ble impacts on the NLO susceptibility. In other words, the remarkable third-order nonlinearities[x（3）≈10 19 m2/V2] mainly come from the [MoI32O372（CH3COO）30（H2O）72]42 anions. This fact reveals that the applications of the NLO active polyoxometalates in various environments（such as hydrophilic, hydrophobic, polar, apolar, etc.） can be achieved by simply varying cations to meet the demands in the design of diverse devices. Keywords Keplerate type polyoxometalate; Nonlinear optical property; Z-Scan technique; Self-defocusing; Reverse saturable absorption     

一个新型层状化合物[Ni(C10H8N2)2V3O8.5]的水热合成与晶体结构

多金属氧酸盐因其在医药临床、工业催化和功能材料等方面的广泛应用而引起人们的关注[1～7]. 由于钒化合物具有令人感兴趣的结构以及在材料领域中的重要的应用而倍受关注. 在以往的合成中, 常压溶液合成是主要手段, 利用水热合成方法制备多金属氧酸盐配合物晶体是近几年来国际上刚刚兴起的一项研究工作, 通过该方法已合成出一批具有新颖结构的层状、链状、多孔、高聚合度化合物[8～11], 一些已用于药物和催化剂的研究工作中. V-O体系化合物的合成与表征近来已引起人们的极大兴趣, 如: [VⅣVⅤ2O7(phen)]n[12]是一含有混合价钒的层状结构; Ni(en)3(VO3)2[13], Cu(dien)V2O6*H2O[14]是一维链状结构. 为了探究水热条件下钒物种的反应特性及生成规律, 制备新的钒配合物晶体, 目前我们正在积极开展这方面的研究并取得了一定成果.     

新的四帽Keggin结构的金属-氧簇合物[NiMo12O40H10{Ni(H2O)3}4]的水热合成与结构表征

多金属氧酸盐 (也称金属 -氧簇 )由于在催化、材料及医药等领域的应用日益广泛而备受关注 .近年来 ,一些新颖的非经典结构的化合物不断被合成出来 .如带二帽的 Keggin结构化合物 [V15O4 2 ]9- [1] ,[PV14 O4 2 ]9- [2 ] ,[As V14 O4 2 ]9- [3 ] ,[{ Mo8V7O4 2 } 2 ]14 - [4 ] ,     

Crystal Structure and Photoluminescence Properties of Two Barium(Ⅱ) MOFs

In this article, two Ba(Ⅱ) metal-organic frameworks(MOFs), {[Ba(BPS)(H₂O)₂]·H₂O}_n(1) and[Ba(BPS)(H₂O)₂]_n(2)(H₂BPS=4,4'-bibenzoic acid-2,2'-sulfone), were synthesized and characterized. X-Ray crystal structural analyses reveal that compounds 1 and 2 have different structures, which is probably related to different coordination modes of ligand in compounds 1 and 2. It is remarkable that compounds 1 and 2 both show excellent thermal stability. The solid-state emission spectra reveal that compounds 1 and 2 both present strong luminescence emission bands at room temperature.     

金属有机电荷转移盐(CpFeBz)n[M(L)2](L=mnt或dmit)的合成及其三阶非线性光学性质

合成了两种类型共九个新的金属有机电荷转移盐(CpFeBz)n[M(mnt)2]和(CpFeBz)n[M.(dmit)2](M=Ni, Pd, Pt,Cu, Co; Cp代表环戊二烯基; Bz代表苯; 通过元素分析、IR和1H NMR对化合物进行了鉴定。用简并四波混频的方法首次研究了金属有机电荷转移盐的三阶非线性光学性质。结果表明, 这类金属有机电荷转移有较大的近共振三阶非线性光学响应。     

Structural tuning of coordination polymers by 4-connecting metal node and secondary building process

Due to variation in ligand's conformation, metal node's connecting geometry, and secondary building process by anions, bat-like, dumbell-like, diamondoid, or pillar-layer topologies are achieved.     

Cyano-bridged bimetallic complexes of copper(II) with tetracyanonickelate(II). Crystal structure of [Cu(dpt)Ni(CN)4]

Five new complexes of composition [Cu(dpt)Ni(CN)₄] (1) (dpt=dipropylenetriamine), [Cu(dien)Ni(CN)₄]·2H₂O (2) (dien=diethylenetriamine), [Cu(N,N′-dimeen)Ni(CN)₄]·H₂O (3) (N,N′-dimeen=N,N′-dimethylethylenediamine), [Cu(N,N-dimeen)Ni(CN)₄]·H₂O (4) (N,N-dimeen=N,N-dimethylethylenediamine) and [Cu(trimeen)Ni(CN)₄] (5) (trimeen=N,N,N′-trimethylethylenediamine) have been obtained by the reactions of the mixture of Cu(ClO₄)₂·6H₂O, appropriate amine and K₂[Ni(CN)₄] in water and have been characterized by IR and UV–Vis spectroscopies and magnetic measurements. The crystal structure of [Cu(dpt)Ni(CN)₄] (1) has been determined by single-crystal X-ray analysis. The structure of 1 consists of a one-dimensional polymeric chain ---Cu(dpt)---NC---Ni(CN)₂---CN---Cu(dpt)--- in which the Cu(II) and Ni(II) atoms are linked by CN groups. The nickel atom is four coordinate with four cyanide-carbon atoms (two cyano groups are terminal and two cyano groups (in cis fashion) are bridged) in a square-planar arrangement and the copper atom is five coordinate with two cyanide-nitrogen and three dpt-nitrogen atoms, in a distorted square-pyramidal arrangement. The temperature dependence of magnetic susceptibility (2–300 K) was measured for compound 1. The magnetic investigation showed the presence of a very weak antiferromagnetic interaction (J=−0.16 cm⁻¹) between the copper atoms within each chain through the diamagnetic Ni(CN)₄ ²⁻ ions.     

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.     

Lanthanide and Transition Metal Coordination Polymers via Hydrothermal Reaction

Studies on the syntheses, structures and properties of lanthanide-transition metal complexes are of current great interest, because they can provide good models for investigation of the nature of magnetic exchange interaction between 3d and 41metal ions in the magnetic materials containing rare earth metals. Many of such studies were focused on discrete complexes which were synthesized from the conventional self-assembly reactions in solution. Although several infinite lanthanide-transition metal complexes containing organic ligands have been obtained by conventional solution synthetic method, the polymeric complexes have been poorly explored. Recently we try to use organic ligands for designing magnetic complexes comprising lanthanide and transition metal ions, especially Gd-Cu, Gd-Zn and Gd-Ag couple,with infinite structures, and hope to provide useful messages for the modeling of the magnetic exchange in magnetic materials. Herein reported are a series of lanthanide and transition metal polymeric complexes[{Gd₂M₃(pydc)₆(H₂O)₁₂}·4H₂O]_n and[{Gd₄M₂(pydc)₈(H₂O)₁₂}·4H₂O]_n (M=Cu, Ag,Zn) with 1D chain and 3D wave-like structure, which were prepared from the hydrothermal reactions of Gd₂O₃, pyridine-2,5-dicarboxylic acid (H₂pydc) and Zn(OAc)₂ or MO, respectively.     

铁氰根桥联的一维链状大环配位聚合物的合成及结构

配位聚合物的合成、结构和性质研究近年来引起了人们极大的兴趣 ,已成为配位化学最活跃的研究领域之一 .由于 [Fe( CN) 6 ]3- 和 [Fe( CN) 6 ]4- 离子本身具有丰富的配位特性 ,可与金属离子及其配合物形成一维链状、二维网状和三维立体结构的配位聚合物 [1～ 5] ,铁氰根和亚铁氰根桥联的配位聚合物的研究成为其中的研究热点之一 .此外 ,铁氰根和亚铁氰根桥联的配位聚合物具有较高的铁磁相变温度[6～ 8] ,是一类具有较好应用前景的分子磁体 .但是 ,以金属大环配合物作为结构单元与 [Fe( CN) 6 ]3-和 [Fe( CN) 6 ]4-离子形成的配位聚合物…     

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.     

Coordination Polymers with Bipyridyl Diene and Triene Ligands: Synthesis,Structures and Luminescent Properties

Solvothermal reactions of cadmium salts with bipyridyl diene and triene ligands[1,3-bis((E)-2-(pyridin-4-yl)vinyl)benzene-(1,3-bpeb) and 1,6-bis(4-pyridyl)-1,3,5-hexatriene(bphte)] and one bipyridyl triene ligand[1,6-bis(4-pyridyl)-1,3,5-hexatriene-(bphte)] in the presence of auxiliary carboxylic acids including 2,6-dichlorobenzoic acid(2,6-HDCBA) and 2-naphthal-enecarboxylic acid(2-HNCA) gave rise to four coordination polymers[Cd(bphte)(2,6-DCBA)₂]_n(1), {[Cd(bphte)(2-NCA)₂]·5.8H₂O}_n(2),[Cd₂(1,3-bpeb)₂(2,6-DCBA)₄]_n(3) and {[Cd₄(1,3-bpeb)₄(2-NCA)₇(HCOO)]·     

基于一维[H_2Mo_4O_(14)]_n~(2n-)链和双吡啶双酰胺配体的三维锌配合物的合成、结构与性能

选择柔性的双吡啶双酰胺配体N,N'-双(3-吡啶甲酰胺基)-1,2-乙烷(3-bpye)、钼酸铵和氯化锌在水热条件下自组装制备了一个基于一维[H_2Mo_4O_(14)]_n~(2n-)链的三维锌配合物[Zn(3-bpye)(H_2Mo_4O_(14))(H_2O)_2],并通过元素分析、红外光谱、热重分析等技术手段研究了配合物的结构,并利用X射线单晶衍射分析进行了晶体结构表征。结构解析揭示标题配合物是三斜晶系,P-1空间群,晶胞参数a=0.61310(3)nm,b=1.04750(6)nm,c=1.06540(6)nm,α=78.5540(10)°,β=77.5350(10)°,γ=89.9050(10)°,V=0.65420(6)nm~3,M_r=981.47,D_c=2.491 g/cm~3,Z=1,F(000)=468,R_1=0.0290,ωR_2=0.1068。标题配合物中,金属锌离子连接一维[H_2Mo_4O_(14)]_n~(2n-)链形成一种二维无机双金属层[Zn(H_2Mo_4O_(14))]_n,相邻的层间又通过双齿配体3-bpye连接形成三维CdSO_4拓扑的骨架结构。配合物表现出强的荧光发射特性,而且其在紫外光照下对亚甲基蓝和罗丹明B均有明显的催化降解活性。     

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。