Oligocyanometallic cords as building blocks in luminescent three-dimensional coordination polymers: [Ag4Cd2(tren)2(CN)6.5][Ag(CN)1.5] and [Au2Cd(tren)(CN)4]·H2O

The syntheses, structures and luminescent properties of two unusual mixed-metal coordination polymers, namely [Ag₄Cd₂(tren)₂(CN)_7.5][Ag(CN)_1.5] 1 and [Au₂Cd(tren)(CN)₄]·H₂O 2 (tren = tris(2-aminoethyl)amine), are presented. Both compounds contain abnormal metal cords of oligocyanometallic anions as building blocks wherein the d¹⁰–d¹⁰ interaction plays a crucial role in the metal–metal assembly.     

氰桥化合物[cis-Fe(bpy)2(CN)2Mn(L)]2[PF6]4的合成及其对金属离子选择识别作用

将Mn(Ⅱ)离子、有机配体L(L=1,6-二苯基-2,5-双(2-甲基吡啶基)-2,5-二重氮己烷)和氰基化合物cis-FeⅡ(bpy)2(CN)2·3H2O(bpy=2,2′-联吡啶)在NH4PF6存在下制备一个四元环异核氰桥化合物即标题化合物,并对其结构进行表征。重金属离子对标题化合物的荧光响应研究表明,标题化合物对Cu(Ⅱ)和Fe(Ⅲ)有很好的选择性。随着金属离子Cu(Ⅱ)和Fe(Ⅲ)的加入,标题化合物的荧光强度逐渐降低至基本消失。随着金属离子Pb(Ⅱ)和Fe(Ⅱ)的加入,标题化合物的荧光强度逐渐降低,当金属离子加到一定浓度,标题化合物的荧光强度不随金属离子的变化而变化。对于Co(Ⅱ)、Cr(Ⅲ)、Mn(Ⅱ)、Cd(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)等离子,随着金属离子的加入标题化合物的荧光强度改变甚微或不改变。     

[（C2H5）N4]2{FeS4[S2CN（C2H5）2]4}的晶体和分子结构

本文报导含类立方烷型簇核Ｆｅ４Ｓ４的金硫配位化合物「（Ｃ２Ｈ５）４Ｎ２「Ｆｅ４Ｓ４」Ｓ２ＣＮ（Ｃ２Ｈ５）２」４」的合成,晶体和分子结构测定的结果。     

Cyano-Bridged Heteropolynuclear Ni(II), Cu(II) and Cd(II) Complexes, [M(deten)2Ni(μ-CN)2(CN)2] n

Three new complexes [M(deten)₂Ni(μ-CN)₂(CN)₂] _n (M = Ni, Cu and Cd, deten = N,N-diethylethylenediamine) have been synthesized and characterized by chemical, thermal analysis, FT-IR and Raman spectroscopies. The crystal structure of the Cd complex has been determined by X-ray single crystal diffraction. Structural study reveals that the Ni²⁺ and Cd²⁺ ions are located on inversion centers, and adopt slightly distorted square-planar and octahedral geometries, respectively. In the crystal structure, the intermolecular N–H⋯N hydrogen bonds link the polymeric chains into a two dimensional network. Vibrational spectral data indicate the presence of two ν(C≡N) for complexes can be assigned to the terminal and bridging cyanides. The decomposition reaction take places in the temperature range 30–1000 °C in the static air atmosphere.     

铁镍双金属配合物[Fe(2,2’–bpy)2Ni(CN)4]n的合成、晶体结构及磁性EI北大核心CSCD

使用K3[Fe(CN)6]提供氰基阴离子和Fe2+阳离子,与Ni(Ac)2·4H2O和2,2’–联吡啶(2,2’–bpy)在水热条件下反应制备了氰基桥连的双金属铁镍配合物[Fe(2,2’–bpy)2Ni(CN)4]n(1),用红外光谱、热重分析和X射线衍射对其进行表征。结果表明:在配合物1中,[Fe(2,2’–bpy)2]2+阳离子和[Ni(CN)4]2–阴离子通过氰基桥联形成Fe2+、Ni2+离子交替存在的一维锯齿链[Fe(2,2’–bpy)2Ni(CN)4]n,热重分析显示,双金属配合物[Fe(2,2’–bpy)2Ni(CN)4]n有较好的热稳定性,磁性测量表明,配合物[Fe(2,2’–bpy)2Ni(CN)4]n中金属铁镍离子间存在强的反铁磁相互作用。     

Structures and magnetism of bimetallic octacyanometallates: honeycomb-like [Mo(CN)8Ni2(pn)4]n·4nH2O and binuclear [Mo(CN)8Ni(en)2(H2O)][Ni(en)3]·2H2O (pn=1,3-diaminopropane,en=1,2-diaminoethane)

Bimetallic octacyanometallates [Mo(CN)₈Ni₂(pn)₄]_n·4nH₂O (1) and [Mo(CN)₈Ni(en)₂(H₂O)][Ni(en)₃]·2H₂O (2) based on [Mo(CN)₈]⁴⁻ were synthesized in aqueous solution, and their crystal and molecular structures have been determined. The complex [Mo(CN)₈Ni₂(pn)₄]_n·4nH₂O (1) consists of novel two-dimensional honeycomb-like layers. The complex [Mo(CN)₈Ni(en)₂(H₂O)][Ni(en)₃]·2H₂O (2) contains a binuclear anion [Mo(CN)₈Ni(en)₂(H₂O)]²⁻,[Ni(en)₃]²⁺ cation and two lattice water molecules. Magnetic studies suggest a possible weak antiferromagnetic interaction between Ni²⁺ ions in 1.     

Synthesis and crystal structure characterization of Cu ( Ⅰ ) coordinational polymer {Cu(4,4'-bipy)Br}n

利用溶剂热法合成了标题化合物,其结构经元素分析和X-射线单晶衍射表征.标题化合物属于四方晶系,I41/acd空间群,晶胞参数:a=1.4443(4)、b=1.444 3(4)、c=3.855 0(15) nm、V=8.042(4) nm3、Z =32、Mr=299.63 g/mol、Dc=1.980 g·cm-3、μ =6.10 mm-1、F(000) =4 672、R1 =0.029、wR2=0.079、S=1.05.标题化合物中Cu+分别与两个4,4'-联吡啶上一个N原子配位以及两个端基溴原子配位,形成了四面体配位几何构型.分子内Cu…Cu之间的距离为0.282 95 (13) nm.在a+c轴方向,通过4,4’-联吡啶桥联作用形成二维层状网格,层与层通过互穿插形成三维结构.     

Two inorganic–organic hybrid compounds based on [Ni2(V3O9)2]2− cluster and {Co2V2} cage subunits

Two novel inorganic-organic hybrid compounds (Ni₃(Hfcz)₄(V₃O₉)₂? 2H₂O) (1) and Co₅(H₂O)₄(fcz)₂(V₄O₁₂)₂ (2) have been successfully constructed, based on [Ni₂(V₃O₉)₂]^2? “bow tie” clusters and {Co₂V₂} pure inorganic cages. Structural analysis reveals that the clusters and cages are expanded to a 2D network and 3D framework via Ni^II and Co^II, respectively. In addition, we investigated the optical band gaps of the two compounds: 2.92 eV and 2.23 eV.     

铁镍双金属配合物[Fe(2,2’–bpy)_2Ni(CN)_4]_n的合成、晶体结构及磁性

使用K_3[Fe(CN)_6]提供氰基阴离子和Fe~(2+)阳离子,与Ni(Ac)_2·4H_2O和2,2’–联吡啶(2,2’–bpy)在水热条件下反应制备了氰基桥连的双金属铁镍配合物[Fe(2,2’–bpy)2Ni(CN)_4]_n(1),用红外光谱、热重分析和X射线衍射对其进行表征。结果表明:在配合物1中,[Fe(2,2’–bpy)_2]~(2+)阳离子和[Ni(CN)_4]~(2–)阴离子通过氰基桥联形成Fe~(2+)、Ni~(2+)离子交替存在的一维锯齿链[Fe(2,2’–bpy)_2Ni(CN)_4]_n,热重分析显示,双金属配合物[Fe(2,2’–bpy)_2Ni(CN)_4]_n有较好的热稳定性,磁性测量表明,配合物[Fe(2,2’–bpy)_2Ni(CN)_4]_n中金属铁镍离子间存在强的反铁磁相互作用。     

Synthesis and Crystal Structure of an One-dimensiornal Silver(Ⅰ)Sulfonate Complex [Ag2 (2-Pyr) ( H2O)4 ]L2

由Ag2 CO3、2,5-二氯-4-氨基苯磺酸(HL)和2-甲基吡嗪(2-Pyr)反应,得了一种新型磺酸银配合物[Ag2(2-Pyr)( H2O)4]L2(1),通过元素分析、红外光谱和X-单晶衍射等对配合物的结构进行了表征.结果表明:1属单斜晶系,空间群P21/c,晶胞参数a＝0.92748(19),b=0.77156(15),c＝2.0044(4) nm,β=91.34(3)°,V＝ 1.4340(5) nm3,Z＝2,F(000)＝850,Dc＝ 1.999 g/cm3,R＝0.0867,wR2＝0.1717 [I＞2σ(I)].配合物中银离子被2-Pyr配体和配位水分子连接成一维的链状结构,进一步通过分子间氢键作用扩展为三维的超分子结构.并且得出了第二配体(2-Pyr)的存在使磺酸银化合物的结构发生了根本的改变.     

Electronic Switch in the Carbon-Centered [Re12CS17(CN)6] n− Nanocluster

An abrupt change in internuclear Re–Re distances between {Re₆} subunits in the carbon-centered [Re₁₂μ₆-CS₁₇(CN)₆] ⁿ⁻ complexes caused by the change of the oxidation state (n = 6, 8) is first theoretically shown to be possibly controlled by an external electric field. ¹³C NMR signal is shown to change over ~400 ppm (~37G) for μ₆-C atom together with n. Thereby, the metal cluster [Re₁₂μ₆-CS₁₇(CN)₆] ⁿ⁻ can be considered as a perspective model of a molecular switch.     

Synthesis,crystal structure and magnetic properties of one-dimensional cyano-bridged bimetallic complex of [Mn(Me2-bipy)2]3[W(CN)8]2·9H2O

An octacyanotungstate(V)-manganese(II) bimetallic assembly [Mn(Me₂-bipy)₂]₃[W(CN)₈]₂·9H₂O (1) (Me₂-bipy = 4,4′-dimethyl-2,2′-bipyridine) was synthesized in methanol and characterized by X-ray crystallography. X-ray analysis shows that complex 1 is a neutral, one-dimensional (1D) infinite chain polymer. Magnetic data analysis demonstrates a long-range magnetic interaction and two different antiferromagnetic coupling constants obtained by fitting between Mn and W ions in 1.     

Synthesis and structure of [{As(NtBu)3}2Li6] containing an [As(NtBu)3]3− trianion

Attempts to prepare the [As(N^tBu)₃]³⁻ trianion by the reaction of As(NMe₂)₃ with [^tBuNHLi]_n (1:3 monomer equiv.) proved unsuccessful. However, if the reaction is carried out with an excess of ^tBuNH₂ (3 equiv.) the target complex [{As(N^tBu)₃}₂Li₆] (1) is obtained. This is the first example of a complex containing an [As(NR)₃]³⁻ trianion.     

Synthesis,structure of a coordination polymer: {Na2[Zn(C2O4)1.5H2PO4] · 2H2O}n

A phosphatooxalate compound {Na₂[Zn(C₂O₄)_1.5H₂PO₄] · 2H₂O}_n 1 was synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction, IR spectroscopy, thermal gravimetric analysis (TGA) and fluorescent spectroscopy. X-ray single-crystal analysis revealed that its structure was a new mixed inorganic–organic ligand supramolecular framework building up through multilayer assembly.     

Two novel 2D organic–inorganic hybrid silicotungstates assembled by {Cu2Ln2(ox)(SiW11)2} dimers and [Cu(en)(ox)]/[Cu(en)2] linkers

Two novel 2-D organic–inorganic hybrid silicotungstates [H₂en][Cu(en)₂(H₂O)]₂{[Cu(en)₂]₃[Cu(en)(ox)]₂[Ln₂(ox)(α-SiW₁₁O₃₉)₂]}·nH₂O (Ln = Er^III, n = 10 for 1, Ln = Sm^III, n = 8 for 2) with mixed organic ligands of ox and en (ox = oxalate, en = ethylenediamine) have been hydrothermally synthesized and characterized by IR spectrum, thermogravimetric analysis (TGA), power X-ray diffraction (PXRD) and X-ray single-crystal diffraction, respectively. Notably, 1 and 2 are isomorphic and exhibit the first novel 2D organic–inorganic hybrid silicotungstates assembled by {Cu₂Ln₂(ox)(SiW₁₁)₂} dimers and [Cu(en)(ox)]/[Cu(en)₂] linkers. Furthermore, the TG curve of 1 and 2 display three steps of weight loss in the range of 25–1000 °C.     

[Ru(bpy)_2dppz]~(2+)的合成及其与DNA的相互作用研究

首先通过两步反应合成了"光开关"分子,[Ru(bpy)2dppz]2+(简称Ru-dppz; bpy=2,2'-联吡啶,dppz=二吡啶[3, 2-a; 2', 3'-c]吩嗪),并分别用紫外-可见吸收光谱法、核磁共振和质谱表征其结构。再利用荧光法考察了Ru-dppz与双链DNA(dsDNA)的相互作用。结果表明:随着Ru-dppz与dsDNA的结合,Ru-dppz荧光强度增加。根据荧光滴定实验结果,计算所得Ru-dppz与dsDNA的结合常数为1.5×107L/mol,结合比为0.14。     

2-{4-[2-(吩噁嗪-10-基)乙氧基]苄基}-丙二酸二甲酯的合成

2 {4 [2 (吩口恶嗪 10 基 )乙氧基 ]苄基 } 丙二酸二甲酯是一种对Ⅱ型糖尿病有较高活性的化合物 ,活性较市场上药效最好的罗格列酮高 ,且具有PPARα、PPARγ双活性。文献报道的合成方法 ,使用了 2 溴乙醇、对卞氧基苯甲醛等价格昂贵 ,不易获得的原料 ,且反应过程需要高压条件。作者引入了相转移催化方法 ,所用原料为1,2 二溴乙烷等 ,价格便宜 ,且易于获得 ,反应条件为常温常压 ,降低了生产成本     

Synthesis,structure and magnetic properties of a trinuclear cyano-bridged complex [Cu(bappz)(μ-NC)Ni(CN)2(μ-CN)Cu(bappz)](ClO4)2 {bappz=1,4-bis(3-aminopropyl)piperazine}

The bimetallic trinuclear complex [Cu(bappz)(μ-NC)Ni(CN)₂(μ-CN)Cu(bappz)](ClO₄)₂ (bappz=1,4-bis(3-aminopropyl)piperazine) has been prepared from the reaction of [Cu(bappz)](ClO₄)₂ and K₂[Ni(CN)₄] in water and its crystal and molecular structure has been determined. The structure consists of a trinuclear [Cu(bappz)(μ-NC)Ni(CN)₂(μ-CN)Cu(bappz)]²⁺ cation and two perchlorate anions. The bridging [Ni(CN)₄]²⁻ anion is coordinated by two [Cu(bappz)]²⁺ cations through two cyano groups, providing a novel trinuclear structure with the Cu–(NC)–Ni–(CN)–Cu linkage. The nickel(II) ion is four-coordinated by carbon atoms from four cyano groups (two of them, in trans position, form a bridge) in a square planar arrangement, whereas both the copper(II) ions are five-coordinated by four bappz nitrogens and one cyanide nitrogen in a distorted square–pyramidal geometry. The temperature dependence of magnetic susceptibility was measured for this compound over the range of 2–300 K. The magnetic investigation showed the presence of a very weak antiferromagnetic interaction (superexchange interaction parameter J=−0.54 cm⁻¹) between the copper atoms through the diamagnetic [Ni(CN)₄]²⁻ ion.