一种新型α-二亚胺钠化合物（英文）

碱金属钠与异丙基α-二亚胺在乙二醇二甲醚溶液中通过发生氧化还原反应生成异丙基α-二亚胺钠金属有机化合物[Na(DME)L](L=[(2,6-i Pr_2C_6H_3)NC(Me)]_2).利用X射线单晶衍射分析了该化合物的晶体结构,其晶体结构是一个含有-1价阴离子自由基配体的1∶1[Na L]结构单元.利用电子顺磁共振(EPR)手段对该化合物的电子结构进行了研究.     

N,N,N′,N′,-(四环己基-3-氧戊烷)二酰胺的晶体结构

双酰胺开链冠醚由于合成方便,络合性能好而引起人们的兴趣.Simon等合成了N,N,N′,N′-(四环己基-3-氧戊烷)二酰胺和它的Ca~(2 ),Mg~(2 )络合物,但未见关于配体晶体结构的报道.我们开展了有关这类化合物的合成及应用研究.本文报导标题化合物的晶体结构.     

以三乙烯二胺为配体的过渡金属配位化合物合成、晶体结构及荧光性质研究

采用混合溶剂热法合成出一系列以三乙烯二胺(简写dabco)为配体的新型过渡金属配位化合物[CdCl3H(dabco)2](1)、[CoCl3Hdabco](2)、[NiCl2(H2O)3Hdabco]Cl(3)和[CuCl3H(dabco)2]Cl·H2O(4)。对该系列化合物进行了元素分析、红外光谱以及热重分析表征,并通过X射线单晶衍射分析确定出晶体结构。结构解析表明:化合物1具有一维直链状分子结构;化合物2具有一维左螺旋状分子结构,化合物3具有一维右螺旋链状分子结构;化合物4具有二维平面网格状分子结构。对该系列化合物的荧光光谱研究结果表明,化合物1~4均具有较好的荧光性质。     

超分子化合物[CO(bppdca)_2(HL)_2(H_2O)_2]·2H_2O]的晶体结构和性质

以N,N′-二(3-吡啶基)-吡啶-3,5-二甲酰胺(bppdca)和1,4-环己烷二羧酸(H2L)为混合配体,利用水热合成方法获得了一个三维的超分子化合物[CO(bppdca)2(HL)2(H2O)2]·2H2O],并通过元素分析、IR和单晶X射线衍射技术确定了该化合物晶体结构.结构分析表明该化合物属单斜晶系,P21/n空间群,晶胞参数a=0.820 65(6)nm,b=1.259 76(9)nm,c=2.479 11(18)nm,β=98.061 0(10)°,Z=2,V=2.537 6(3)nm3,Mr=1 111.98,Dc=1.455g/cm3,F(000)=116 2,μ=0.421mm-1,S=1.018,R=0.041 7,wR=0.102 3.晶体结构分析表明,配合物中的CoⅡ与2个bppdca配体、2个HL阴离子以及2个配位水分子形成单金属配合物.相邻的配合物通过氢键作用拓展成三维超分子框架.另外,也研究了该化合物的热稳定性、荧光性质以及光催化性质.     

一种新颖酰基硫脲金属簇合物的合成与晶体结构

报道了一种新型酰基硫脲金属簇合物[Cu₆(HL)₆] (HL＝N-乙氧羰基-N'-4-氟苯基硫脲)的合成和晶体结构. 对化合物用元素分析、红外光谱、核磁共振谱、差热-热重分析确定了配合物的组成, 并经X射线单晶衍射法确定了其单晶结构. 晶体结构表明, 该化合物属于三斜晶系, 空间群, a＝1.2508(11) nm, b＝1.3011(11) nm, c＝1.4686(12) nm, a＝102.401(14)°, β＝97.859(2)°, γ＝114.700(13)°, V＝2.051(3) nm³, Z＝1, D_c＝1.687 Mg/m³. 标题化合物是由六个铜离子和六个硫脲配体组成的笼状金属簇合物, 每一个硫脲配体上与乙氧酰基相连的氮原子与铜进行配位, 并且配体上硫羰基上的硫原子与铜也发生配位作用, 使它们互相连接形成畸变的多面体结构.     

N,N,N′,N′-四(2-苯并咪唑亚甲基)-1,2-乙二胺的晶体和电子结构

合成了六齿配体N,N,N′,N′-四(2-苯并咪唑亚甲基)-1,2-乙二胺(EDTB).对该配体进行了元素分析、紫外和红外表征;采用X射线衍射方法测定了晶体结构,依据晶体结构数据使用G98程序对配体进行了量子化学计算.     

含吡唑配体的VIB金属羰基配合物的合成与电化学性质研究

研究了吡唑类配体与M(CO)6(M=Cr,W)的光化学反应,合成了一系列的含吡唑配体的五羰基铬钨配合物。研究了该类化合物的电化学性质。结果表明：铬系列化合物存在一对准可逆的氧化还原峰,而钨系列化合物只存在一个不可逆的氧化峰,用X射线单晶衍射测定了化合物3,4,5－三甲基吡唑五羰基铬的晶体结构。该晶体为单斜晶系,空间群为P2(1)/m,晶胞参数为a=0.9106(3)nm,b=07627(2)nm,c=0.9637(3)nm,β＝91.855(5)°,V=0.6689(3)nm^3,Z=2,R=0.042,Cr为六配位的变形八面体构型。     

九种Salen型多齿新配体的合成

利用乙二胺及其衍生物的Mannich反应在无催化剂的条件下合成了9种Salen型新的配体,化合物1和2在无溶剂条件下合成,化合物3a～3g在Salen配体中引入呋喃杂环,对其与金属的配位提供了多种可能性.所得化合物结构经元素分析,IR,MS,1H NMR等确认,同时用X射线单晶衍射测定了化合物1和3b的晶体结构.     

(Z)-1-[2-(二苯基碘化锡基)乙烯基]-1-环己醇的合成、晶体结构和性质

报道了标题化合物的合成、晶体结构及性质。该晶体属于单斜晶系，空间群为P2~1，晶胞参数a=0.9255(3)nm，b=1.0504(3)nm，c=1.0217(3)nm，β=100.99(2)°，V=0.9750nm^3，Z=2，D~c=1.790g/cm^3，R=0.025，晶体结构由直接法解出。标题化合物分子中的锡原子被配体的三个碳、一个碘和一个氧原子配位；配位原子是畸变的三角双锥构型；标题化合物具有与卤素发生取代反应而不发生加成反应的性质。     

[Fe(N2H5)2(SO4)2]n的合成、结构和磁性质

采用水热合成方法得到一例新的过渡金属铁(Fe)的含肼硫酸盐: [Fe(N₂H₅)₂(SO₄)₂]_n (1). 用单晶X射线衍射的方法对其晶体结构进行了表征. 结果表明, 该化合物以硫酸根为桥连配体, 质子化的肼分子为端基配体, 形成一维(1D)链状结构. 肼分子和硫酸根形成的链间氢键, 将1D链进一步扩展成三维(3D)结构. 磁性测试表明化合物在低温下显示出反铁磁有序的磁行为.     

镧系元素-N,N-二(2-氧吡咯-1-甲基)甘氨酸-邻菲咯啉三元体系的光致变色

采用激发光谱、荧光光谱和紫外 可见光谱研究了镧系元素 N ,N 二 (2 氧吡咯 1 甲基 )甘氨酸 (MPG) 邻菲咯啉 (phen)三元体系的性质。研究了该体系水溶液的光致变色。太阳光或汞灯照射下溶液由黄色转变成绿色 ,而在避光处保存 ,绿色褪去变成黄色溶液。这种光致变色现象与体系的pH值有关     

含有给电子生色团的双马来酰亚胺与脂肪二胺的共聚合及其荧光光谱跟踪

我们曾合成了一系列含有给电子生色团的丙烯酰类单体 ,它的给电子本质主要是由氮原子 ,以Ｎ ,Ｎ 二甲基氨基苯基的形式所贡献[1～ 4] ,即 :Ｎ ( 4 Ｎ′,Ｎ′ 二甲氨基苯基 )马来酰亚胺 ,Ｎ ( 4 Ｎ′ ,Ｎ′ 二甲氨基苯基 )丙烯酰胺 ,Ｎ ( 4 Ｎ′ ,Ｎ′ 二甲氨基苯基 )衣康酰胺 ,甲基丙烯酸 (对 4 Ｎ ,Ｎ 二甲氨基 )苄酯 ,这些单体的荧光发射强度总是远远低于相同浓度聚合物的荧光强度 .为了区别所熟知的荧光浓度自猝灭 ,我们称这种现象为结构自猝灭效应 (ＳＳＱＥ) [1～ 5] .具有ＳＳＱＥ的丙烯酰类单体可表示为Ａ( =) Ｄ( ) 型化合物 …     

Synthesis,crystal and molecular structure of the novel complex [dinitrato{N,N-bis(1–methylbenzimidazol-2–ylmethyl)methylamine}]cobalt(II)

Co(NO3)2·6H2O reacts with N,N-bis(1–methylbenzimidazol-2–ylmethyl)methylamine (Me2L) in MeOH/ Et2O solution at ca. 5°C, yielding a novel, penta-coordinate complex, formulated as [Co(NO3)2(Me2L)], which was characterized by means of structural, spectroscopic and magnetic measurements. The Co atom is coordinated in distorted trigonal bipyramidal geometry by three N and two O atoms. The ligand Me2L is coordinated in a facial mode and two coordinated O atoms from the nitrato ligands are in cis-positions.     

Bond length of perchlorate at different temperatures: X‐ray and neutron comparison

The averages (average deviations from the mean are given in square brackets) of uncorrected Cl—O bond distances in a perchlorate anion from an X‐ray diffraction analysis of (N‐{2‐[bis(pyridin‐2‐ylmethyl)amino]ethyl}pyridine‐2‐carboxamidato)(nitric oxide)manganese perchlorate acetonitrile disolvate, [Mn(C₂₀H₂₀N₅O)(NO)]ClO₄·2CH₃CN or [Mn(PaPy₃)(NO)]ClO₄·2CH₃CN, decrease from 1.447 [4] Å at 10 K to 1.428 [4] Å at 170 K. The 10 K value is close to the neutron value (1.441 [1] Å) at 18 K. Comparisons are made with a second X‐ray study at 30 K [1.444 (8) Å] and to libration‐corrected, density functional theory (DFT), and Cambridge Structural Database (CSD) values.     

The effect of the coordination orientation of N atoms on polymeric structures: synthesis and characterization of one‐ and two‐dimensional CuII coordination polymers based on 4‐amino‐3‐(pyridin‐2‐yl)‐5‐[(pyridin‐3‐ylmethyl)sulfanyl]‐1,2,4‐triazole

Three new one‐ (1D) and two‐dimensional (2D) Cu^II coordination polymers, namely poly[[bis{μ₂‐4‐amino‐3‐(pyridin‐2‐yl)‐5‐[(pyridin‐3‐ylmethyl)sulfanyl]‐1,2,4‐triazole}copper(II)] bis(methanesulfonate) tetrahydrate], {[Cu(C₁₃H₁₂N₅S)₂](CH₃SO₃)₂·4H₂O}_n ( 1 ), catena‐poly[[copper(II)‐bis{μ₂‐4‐amino‐3‐(pyridin‐2‐yl)‐5‐[(pyridin‐4‐ylmethyl)sulfanyl]‐1,2,4‐triazole}] dinitrate methanol disolvate], {[Cu(C₁₃H₁₂N₅S)₂](NO₃)₂·2CH₃OH}_n ( 2 ), and catena‐poly[[copper(II)‐bis{μ₂‐4‐amino‐3‐(pyridin‐2‐yl)‐5‐[(pyridin‐4‐ylmethyl)sulfanyl]‐1,2,4‐triazole}] bis(perchlorate) monohydrate], {[Cu(C₁₃H₁₂N₅S)₂](ClO₄)₂·H₂O}_n ( 3 ), were obtained from 4‐amino‐3‐(pyridin‐2‐yl)‐5‐[(pyridin‐3‐ylmethyl)sulfanyl]‐1,2,4‐triazole with pyridin‐3‐yl terminal groups and from 4‐amino‐3‐(pyridin‐2‐yl)‐5‐[(pyridin‐4‐ylmethyl)sulfanyl]‐1,2,4‐triazole with pyridin‐4‐yl terminal groups. Compound 1 displays a 2D net‐like structure. The 2D layers are further linked through hydrogen bonds between methanesulfonate anions and amino groups on the framework and guest H₂O molecules in the lattice to form a three‐dimensional (3D) structure. Compound 2 and 3 exhibit 1D chain structures, in which the complicated hydrogen‐bonding interactions play an important role in the formation of the 3D network. These experimental results indicate that the coordination orientation of the heteroatoms on the ligands has a great influence on the polymeric structures. Moreover, the selection of different counter‐anions, together with the inclusion of different guest solvent molecules, would also have a great effect on the hydrogen‐bonding systems in the crystal structures.     

Two zinc(II) coordination complexes based on an asymmetric multidentate ligand: syntheses,structures, selective fluorescence sensing of iron(III) ions and thermal analyses

The rational selection of ligands is vitally important in the construction of coordination complexes. Two novel Zn^II complexes, namely bis(acetato‐κO)bis[1‐(1H‐benzotriazol‐1‐ylmethyl)‐2‐propyl‐1H‐imidazole‐κN³]zinc(II) monohydrate, [Zn(C₁₃H₁₅N₅)₂(C₂H₃O₂)₂]·H₂O, ( 1 ), and bis(azido‐κN¹)bis[1‐(1H‐benzotriazol‐1‐ylmethyl)‐2‐propyl‐1H‐imidazole‐κN³]zinc(II), [Zn(C₁₃H₁₅N₅)₂(N₃)₂], ( 2 ), constructed from the asymmetric multidentate imidazole ligand, have been synthesized under mild conditions and characterized by elemental analyses, IR spectroscopy and single‐crystal X‐ray diffraction analysis. Both complexes exhibit a three‐dimensional supramolecular network directed by different intermolecular interactions between discrete mononuclear units. The complexes were also investigated by fluorescence and thermal analyses. The experimental results show that ( 1 ) is a promising fluorescence sensor for detecting Fe³⁺ ions and ( 2 ) is effective as an accelerator of the thermal decomposition of ammonium perchlorate.     

A two‐dimensional CdII coordination polymer based on naphthalenediimide: synthesis,crystal structure and photochromic properties

Naphthalenediimides, a class of organic dyes with an expanded π‐electron‐deficient plane, have attracted considerable interest because of their photoinduced electron transfer from neutral organic moieties to stable anionic radicals. This makes them excellent candidates for organic linkers in the construction of photochromic coordination polymers. Such a photochromic two‐dimensional coordination polymer has been prepared using N,N′‐bis(pyridin‐4‐ylmethyl)naphthalene‐1,8:4,5‐bis(dicarboximide) (DPMNI). In crystallization tubes, upon slow diffusion of an MeOH solution of cadmium perchlorate into a CHCl₃ solution of DPMNI, the complex poly[[bis[μ₂‐2,7‐bis(pyridin‐4‐ylmethyl)benzo[imn][3,8]phenanthroline‐1,3,6,8(2H,7H)‐tetrone‐κ²N:N′]bis(perchlorato‐κO)cadmium(II)] chloroform tetrasolvate], {[Cd(C₂₆H₁₆N₄O₄)₂(ClO₄)₂]·4CHCl₃}_n, (I), was obtained. The asymmetric unit contains one Cd²⁺ cation, two DPMNI ligands, two coordinated ClO₄⁻ anions and four CHCl₃ solvent molecules. Each Cd²⁺ cation is interconnected by four DPMNI linkers to generate a neutral two‐dimensional naphthalenediimide coordination network with all the ClO₄⁻ anions above or below this plane. Strong interlaminar anion–π interactions between the coordinated ClO₄⁻ anions and the imide rings of an adjacent layer lead to a three‐dimensional supramolecular structure. Compound (I) exhibits reversible photochromic behaviour and photocontrolled tunable luminescence properties, which may originate from the photoinduced electron‐transfer generation of radicals in the DPMNI ligand.     

Effect of Flexible Bis(Benzimidazole) Ligands on the Structures of Cobalt(II) Coordination Polymers Derived from 2,6‐Naphthalenedicarboxylic Acid

The cobalt(II) coordination polymers{[Co(L1)(nda)] · 2H₂O}_n ( 1 ) and [Co(L2)₂(nda)]_n ( 2 ), [L1 = 1,2‐bis(2‐methylbenzimidazol‐1‐ylmethyl)benzene, L2 = 1,4‐bis(5,6‐dimethylbenzimidazol‐1‐ylmethyl)benzene, H₂nda = 2,6‐naphthalenedicarboxylic acid] were hydrothermally synthesized by self‐assembly of cobalt chloride with H₂nda and different semi‐rigid bis(benzimidazole) derivatives and characterized by IR spectroscopy, elemental analysis, and X‐ray single‐crystal diffraction. Complex 1 displays a 2D layer with (4,4) topology, complex 2 exhibits a 1D infinite chain structure, both complexes were further packed into 3D and 2D supramolecular architectures by weak hydrogen bonding. The catalytic activities of the complexes for degradation of Congo red in a Fenton‐like process are presented. In addition, the electrochemical and electrocatalytical behavior of CPEs modified with both cobalt complexes (Co‐CPE) were investigated in detail.     

The Pyridazine Scaffold as a Building Block for Energetic Materials: Synthesis,Characterization, and Properties

In the present studies, the synthesis of new energetic materials based on the pyridazine scaffold and their characterization is the main subject. For this purpose, desired 3,5‐dimethoxy‐4,6‐dinitropyridazine‐1‐oxide ( 7 ) was synthesized in the first instance. The persubstituted pyridazine precursor laid the groundwork for further preparative modification. The targeted functionalization through the regioselective introduction of various smaller amine nucleophiles such as methylamine or 2‐aminoethanol gave several new energetic materials. Among them are 3,5‐bis(methylamino)‐4,6‐dinitropyridazine‐1‐oxide ( 8 ), 3,5‐bis(methylnitramino)‐4,6‐dinitropyridazine‐1‐oxide ( 9 ), 3,5‐bis(dimethylamino)‐4,6‐dinitropyridazine‐1‐oxide ( 10 ), and 3,5‐bis((2‐hydroxyethyl)amino)‐4,6‐dinitropyridazine‐1‐oxide ( 11 ). With the aim of increasing the detonation performance, compound 8 was additionally nitrated and 3,5‐bis(methylnitramino)‐4,6‐dinitropyridazine‐1‐oxide ( 9 ) was obtained. These new energetic materials were characterized and identified by multinuclear NMR (¹H, ¹³C, ¹⁴N, ¹⁵N) and IR spectroscopy, elemental analysis and mass spectrometry. In addition, their sensitivities toward impact, friction and electrostatic discharge were thoroughly examined. Furthermore, obtained single‐crystals of the substances were characterized by low‐temperature single‐crystal X‐ray diffraction.     

Synthesis,Crystal Structure,Antioxidation and DNA‐Binding Studies of a Zinc(II) Complex with the Bis(N‐allylbenzimidazol‐2‐ylmethyl)aniline

A complex of zinc(II) picrate (pic) with bis(N‐allylbenzimidazol‐2‐ylmethyl)aniline (abba), with composition [Zn(abba)₂](pic)₂, was synthesized and characterized by elemental analysis, electrical conductivity, IR and UV/Vis spectral measurements. The crystal structure of the zinc(II) complex has been determined by single‐crystal X‐ray diffraction. The Zn(II) is bonded to two abba ligands through four benzimidazole nitrogen, resulting in a distorted tetrahedron geometry. The DNA‐binding properties of the ligand and the zinc(II) complex were investigated by electronic absorption, fluorescence spectra and viscosity measurements. The experimental results suggest that the zinc(II) complex binds to DNA in an intercalation mode. In addition, the ligand abba and Zn(II) complex have scavenging effects for hydroxyl radicals and the complex shows stronger scavenging effects for hydroxyl radicals than the ligand.