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1.
具有可逆颜色变化和适当变色寿命的光致变色材料对于无墨水和可擦除打印技术十分重要。我们将1,4,5,8-萘四羧酸二酐与甲硫氨酸结合,设计了一种基于 1,4,5,8-萘二酰胺(NDI)的桥联有机配体(H2ncm),并以 Zn2+和 H2ncm为原料,通过溶剂热反应合成了2种配位聚合物。化合物[Zn(ncm)(H2O)4]·2DMF (1)包含1个Zn2+、1个ncm2-配体、4个配位水分子和2个DMF分子。Zn2+处于八面体的配位环境中,并通过 ncm2-配体连接形成链状结构。化合物[Zn2(ncm)2(H2O)4] (2)包含 2个 Zn2+、2个 ncm2-配体和4个配位水分子。2个Zn2+原子通过2个羧基桥联形成双核结构,并进一步通过ncm2-配体连接形成二维层结构。2显示出从黄色到深棕色的光致变色现象。这种光诱导产生的颜色可以稳定至少3周,但在70 ℃加热时在5 min内即可恢复本来的颜色。我们证明了这种光致变色是源于光照射下NDI·自由基的产生。  相似文献   

2.
Gd2O3,Zn(CH3COO)2·2H2O和吡啶-2,5-二羧酸(H2pydc)的水热反应导致一个新颖的钆-锌配位聚合物[La2Zn2(pydc)5(H2O)2]n(1)。化合物1的晶体属单斜晶系,空间  相似文献   

3.
利用刚性含咪唑基三脚架配体1,3,5-三咪唑基苯(tib)和不同的苯二酸与金属盐反应, 得到一系列具有有趣拓扑结构的配位聚合物, 二酸配体、抗衡阴离子等对结构有很大影响. 将1,2,4,5-苯四酸(H4btec)引入到反应体系, 研究了与不同金属氯化物的反应, 考察了中心金属配位构型等对配合物结构的影响. 分别将NiCl2·6H2O、CoCl2·6H2O、ZnCl2与tib、H4btec、NaOH混合后在水热条件下反应, 得到了三个新的配位聚合物[Ni2(tib)2(btec)]·2H2O (1), [Co2(tib)2(btec)]·2H2O (2), [Zn4(tib)2(btec)Cl4]·2H2O (3). 通过元素分析、红外光谱和单晶结构解析等手段对配合物进行了表征. 化合物1和2具有相同的结构. 在1中, 中心金属Ni(II)采用变形八面体配位构型. 每个btec4-配体连接四个Ni(II)形成无限延伸的一维链状结构, 而每个tib连接三个Ni(II)形成具有典型63-hcb拓扑结构的二维层状结构. 二维层在空间上通过btec4-连接形成最终的层柱状三维结构. 我们对化合物1进行了拓扑分析. 每个Ni(II)链接三个tib和两个btec4-, Ni(II)可以看成是一个五节点. 每个tib和btec4-可以分别被简化成三节点和四节点. 化合物1是一个具有 (3,4,5)-三节点的三维网络结构, 它的Schläfli符号为(4·63·86)2(42·84)(63)2. 进一步分析结果显示, 化合物1中有由两个btec4-、两个Ni(II)和两个tib形成的大环与二维63-hcb层中的大环互相贯穿, 没有交点, 是少有报道的具有自贯穿结构特征的配位聚合物. 化合物3与1, 2的最大区别在于抗衡阴离子Cl-参与到了3的结构中. 结构单元中两个不同的Zn(II)原子(Zn1和Zn2)均采用变形四面体配位构型. 每个btec4-连接六个Zn(II)原子形成一维链状结构. Zn-btec一维链 在空间上沿着两个互相垂直的方向无限延伸. 另外, 每个tib连接三个Zn(II)原子并通过[Zn2(COO)2]双核单元连接形成一维链. 这些链互相连接形成最终的三维结构. 如果将双核单元、Zn2、tib、btec4-分别看做4-、3-、4-、3-节点, 拓扑分析结果表明化合物3是一个具有(3,4)-节点的三维网络, 它的Schl?fli符号为(4·82)2(84·10·12). 热重分析结果表明化合物1~3都有较高的热稳定性. 另外, 化合物3是含d10金属化合物, 荧光测试结果显示3在408 nm处有荧光发射, 可归结于配体内部π-π*电子跃迁, 因为单独的tib在405 nm处有荧光发射. 在1和2中, Ni(II)和Co(II)都采用六配位八面体配位构型, 而在3中Zn(II)采用了四配位四面体配位构型. 另外btec4-不同的配位模式导致在1~3中不同M-btec(中心金属)链的形成. tib与中心金属离子在1和2中形成二维层, 而在3中形成一维链. 通过化合物1~3的结构比较, 可以看到中心金属配位构型和羧基配体配位模式对配合物结构有很大的影响.  相似文献   

4.
使用H2L配体(H2L=5-(1,3-dioxo-1H-benzoisoquinolin-2(3H)-yl) isophthalic acid)和Zn2+通过水热反应,合成了一例基于双核{Zn2(COO)4}次级构筑单元的二维发光配位聚合物[Zn2(L)2(DMSO)2(DMF)](1)(DMSO=二甲亚砜,DMF=N,N-二甲基甲酰胺)。拓扑分析表明1结构中的双核{Zn2(COO)4}单元可视为4连接节点,并与作为连接子的L2-形成(4,4)-网拓扑构型。1表现出对Fe3+离子的选择性发光猝灭响应,检测限为2.8 μmol·L-11对Fe3+的检测具有良好的抗干扰性,且可通过DMF溶剂洗涤实现再生,可多次循环使用。  相似文献   

5.
李策  郗既明  卢振中  张锐  黄岭 《无机化学学报》2023,39(12):2425-2431
具有可逆颜色变化和适当变色寿命的光致变色材料对于无墨水和可擦除打印技术十分重要。我们将1,4,5,8-萘四羧酸二酐与甲硫氨酸结合,设计了一种基于1,4,5,8-萘二酰胺(NDI)的桥联有机配体(H2ncm),并以Zn2+和H2ncm为原料,通过溶剂热反应合成了2种配位聚合物。化合物[Zn(ncm)(H2O)4]·2DMF (1)包含1个Zn2+、1个ncm2-配体、4个配位水分子和2个DMF分子。Zn2+处于八面体的配位环境中,并通过ncm2-配体连接形成链状结构。化合物[Zn2(ncm)2(H2O)4] (2)包含2个Zn2+、2个ncm2-配体和4个配位水分子。2个Zn2+原子通过2个羧基桥联形成双核结构,并进一步通过ncm2-配体连接形成二维层结构。2显示出从黄色到深棕色的光致变色现象。这种光诱导产生的颜色可以稳定至少3周,但在70 ℃加热时在5 min内即可恢复本来的颜色。我们证明了这种光致变色是源于光照射下NDI·自由基的产生。  相似文献   

6.
本文合成了9种含有由天然D(+)-樟脑衍生的1R,3S-1,2,2-三甲基-1,3-环戊二胺(A)为配体的铂(Ⅱ)配合物[Pt(Ⅱ)AX]{其中,X=(CH2)3C(COO-)2(1,1-环丁烷二羧酸根),2CH3OCH2COO-,2CH3CH2OCH2COO-,2CH3(CH2)3OCH2COO-,[OCH(CH3)COO]2-(乳酸根),(OCH2COO)2-(乙醇酸根),2CH3OCH2CH2OCH2COO-,2CH3CH2OCH2CH2OCH2COO-和2CH3(CH2)3OCH2CH2OCH2COO-}。通过元素分析、热重分析、红外光谱、1H核磁共振谱和电喷雾质谱等对配合物进行了表征。体外生物活性测试表明,部分配合物对A549人肺癌细胞和HCT-116人结肠癌细胞具有较强的抗肿瘤活性。  相似文献   

7.
在溶剂热条件下,以2-吡啶甲醛肟(HL)为主配体,Zn(OAc)2·2H2O和NiCl2·6H2O为金属盐,合成了一个Ni2Zn2簇配合物[Ni2Zn2(L)4Cl2(CH3O)2](1),通过元素分析、红外光谱、单晶X射线衍射等对其结构进行了表征。研究了该配合物的磁性及光催化降解染料的性能,结果表明:配合物1属于正交晶系,Pna21空间群,其分子中包含2个Ni离子,2个Zn离子,4个L-配体,2个Cl-离子和2个CH3O-离子。磁性研究表明Ni…Ni离子间存在弱的反铁磁相互作用。光催化降解染料的研究结果表明该配合物对甲基橙和罗丹明B有较好的降解活性,降解率分别达到83.9%和71.1%。进一步探讨了光催化降解染料的作用机理。  相似文献   

8.
使用H2L配体(H2L=2-(1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl) terephthalic acid)和Zn2+通过水热反应,合成了一例基于双核{Zn2(COO)4}次级构筑单元的二维发光配位聚合物[Zn2(L)2(DMSO)2(DMF)](1)(DMSO=二甲亚砜,DMF=N,N-二甲基甲酰胺)。拓扑分析表明1结构中的双核{Zn2(COO)4}单元可视为4连接节点,并与作为连接子的L2-形成(4,4)-网拓扑构型。1表现出对Fe3+离子的选择性发光猝灭响应,检测限为2.8 μmol·L-1。1对Fe3+的检测具有良好的抗干扰性,且可通过DMF溶剂洗涤实现再生,可多次循环使用。  相似文献   

9.
基于二茂铁羧酸配体的镉配合物的合成及结构研究   总被引:1,自引:0,他引:1  
以二茂铁甲酸根FcCOO-(Fc=(η5-C5H5)Fe(η5-C5H4))为主要配体,合成了3个新的配合物[Na2Cd( μ32-FcCOO-)222-FcCOO-)2(CH3OH)2]n (1)、[Cd(phen)(FcCOO-)(η2-FcCOO)(H2O)](phen=邻菲咯啉) (2)、[Cd(Det)(η2-FcCOO-)(FcCOO-)](H2O)2(Det=二乙撑三胺) (3)。测定了配合物的晶体结构。配合物1为单斜晶系,C2/c空间群,二茂铁甲酸根采用μ32-FcCOO-和μ22-FcCOO-的配位方式将Cd2+和Na+连接成一维无限链状结构。配合物23均为单核结构,单斜晶系,P21/c空间群,二茂铁甲酸根都采用 FcCOO-和η2-FcCOO-的方式配位。2中phen以双齿螯合形式配位,水分子参与配位,中心镉离子配位数为6。3中Det以三齿螯合形式配位,中心镉离子配位数也为6,但水分子未参与配位。  相似文献   

10.
(S)-N-二茂铁甲基苯丙氨酸钠为配体,与Zn(Ac)2反应合成了一个新型手性单核配合物(S)-[Zn(FcCH2NHCH(CH2Ph)COO)2·H2O](H2O)。X-射线单晶结构分析表明,中心离子Zn(Ⅱ)与2个FcCH2NHCH(CH2Ph)COO-和1个水分子配位,形成树状的骨架构型。该配合物晶体属正交晶系,P212121空间群。晶胞参数为:a=0.893 4(2) nm;b=1.669 8(4) nm;c=2.588 4(6) nm。电化学测试表明该配合物的氧化和还原峰电位同配体相比向高电位方向移动。室温下,标题化合物呈现出较强的固体双重荧光性能,量子化学计算给出了初步的解释。  相似文献   

11.
《Solid State Sciences》2004,6(11):1287-1294
In order to study new and convenient sol–gel syntheses to homogeneous nanocomposites systems based on zinc sulphide clusters embedded in films of silica glass, a thiourea-functionalized silane ((EtO)3Si(CH2)3NHC(S)NHPh, SilTu) was investigated as starting precursor. Electrospray ionization mass spectrometry (ESI-MS), FT-IR and NMR spectroscopies clearly evidence that SilTu coordinates Zn2+ ions in solution through the thiourea function. Both zinc acetate (Zn(CH3COO)2) and zinc chloride (ZnCl2) were used as zinc source. The SilTuZn2+ complex is also stable under sol–gel conditions. Alcoholic solutions of SilTu, zinc acetate and tetraethoxysilane Si(OEt)4 (TEOS) were used to prepare the thin films by dip-coating. Transparent, homogeneous and crack-free layers were obtained under annealing up to 600 °C. The samples were investigated by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS). Beside ZnS formation, the presence of oxygenated zinc species was observed inside the silica matrix.  相似文献   

12.
Three zinc complexes based on 2,6-bis(N-2-pyridylmethyl)formimidoyl-4-methylphenolate (HL) by employing Zn(ClO4)2, Zn(CH3COO)2, and ZnCl2 have been synthesized and investigated as functional models of phosphoesterases. The molecular structure of [{Zn2L(µ 3-OH)(H2O)}2](ClO4)4 (1) obtained by reacting zinc perchlorate with HL was determined by X-ray diffraction analysis, revealing a tetranuclear species with four zinc centers and two ligands. Two zinc ions are accommodated within the two compartments of each ligand and are bridged by an additional hydroxide leading to Zn–Zn distances of 3.1235(9) and 3.1268(9)?Å, respectively. The hydroxide is involved in an additional bridge to the second LZn2 moiety forming a µ 3-OH. A water molecule is coordinated to two of the four zinc ions. The occurrence of a hydroxide group and of a coordinated water is relevant to the structure found in the native enzyme. The hydrolysis of the phosphoester bis(p-nitrophenol)phosphate ester (BNPP) in a mixture of DMSO and water at 50°C catalyzed by the three zinc compounds has been investigated. High hydrolytic activity was found for all three compounds but differed significantly depending on the nature of the counterion; the chloro derivative was found to be most active, while the perchlorate compound showed the least activity.  相似文献   

13.
New zinc acetate based complex compounds (of general formula Zn(CH3COO)2·1?2L·nH2O) containing one or two molecules of urea, thiourea, coffeine and phenazone were prepared namely: Zn(CH3COO)2·2.5H2O, Zn(CH3COO)2·2u·0.5H2O, Zn(CH3COO)2·tu·0.5H2O, Zn(CH3COO)2·2tu, Zn(CH3COO)2·cof·2.5H2O, Zn(CH3COO)2·2cof·3.5H2O, Zn(CH3COO)2·2phen·1.5H2O. The compounds were characterized by IR spectroscopy, chemical analysis and thermal analysis. Thermal analysis showed that no changes in crystallographic modifications of the compounds take place during (heating in nitrogen before) the thermal decompositions. The temperature interval of the stability of the prepared compounds were determined. It was found that the thermal decomposition of hydrated compounds starts by the release of water molecules. During the thermal decomposition of anhydrous compounds in nitrogen the release of organic ligands take place followed by the decomposition of the acetate anion. Zinc oxide and metallic zinc were found as final products of the thermal decomposition of the zinc acetate based complex compounds studied. Carbon dioxide and acetone were detected in the gaseous products of the decomposition of the compounds if ZnO is formed. Carbon monoxide and acetaldehyde were detected in the gaseous products of the decomposition, if metallic Zn is formed. It is supposed that ZnO and Zn resulting from Zn acetate complex compounds here studied, possess different degree of structural disorder. Annealing takes place by further heating above 600°C.  相似文献   

14.
Spectroscopic (IR), thermoanalytical (TG/DTG, DTA) and biological methods were applied to investigate physicochemical and biological properties of seven zinc(II) complex compounds of the following formula Zn(HCOO)2·2H2O (I), Zn(HCOO)2·tph (II), Zn(CH3COO)2·2H2O (III), Zn(CH3COO)2·tph (IV), Zn(CH3COO)2·2phen (V), Zn(CH3CH2COO)2·2H2O (VI), Zn(CH3CH2CH2COO)2·2H2O (VII), where tph=theophylline, phen=phenazone. The formation of various intermediates during thermal decomposition suggests the dependence on the length of aliphatic carboxylic chain and type of N-donor ligand (tph, phen). The final product of the thermal decomposition was ZnO. The antimicrobial activity of these complexes were tested against G+ and G bacteria. Strong inhibitive effect was observed towards E. coli, salmonellae and Staph. aureus.  相似文献   

15.
The objective of this study is to synthesize ZnO and Mg doped ZnO (Zn1−xMgxO) nanoparticles via the sol-gel method, and characterize their structures and to investigate their biological properties such as antibacterial activity and hemolytic potential.Nanoparticles (NPs) were synthesized by the sol-gel method using zinc acetate dihydrate (Zn(CH3COO)2.2H2O) and magnesium acetate tetrahydrate (Mg(CH3COO)2.4H2O) as precursors. Methanol and monoethanolamine were used as solvent and sol stabilizer, respectively. Structural and morphological characterizations of Zn1−xMgxO nanoparticles were studied by using XRD and SEM-EDX, respectively. Photocatalytic activities of ZnO and selected Mg-doped ZnO (Zn1−xMgxO) nanoparticles were investigated by degradation of methylene blue (MeB). Results indicated that Mg doping (both 10% and 30%) to the ZnO nanoparticles enhanced the photocatalytic activity and a little amount of Zn0.90 Mg0.10 O photocatalyst (1.0 mg/mL) degraded MeB with 99% efficiency after 24 h of irradiation under ambient visible light. Antibacterial activity of nanoparticles versus Escherichia coli ( E. coli ) was determined by the standard plate count method. Hemolytic activities of the NPs were studied by hemolysis tests using human erythrocytes. XRD data proved that the average particle size of nanoparticles was around 30 nm. Moreover, the XRD results indicatedthat the patterns of Mg doped ZnO nanoparticles related to ZnO hexagonal wurtzite structure had no secondary phase for x ≤ 0.2 concentration. For 0 ≤ x ≤ 0.02, NPs showed a concentration dependent antibacterial activity against E. coli . While Zn0.90Mg0.10 O totally inhibited the growth of E. coli , upper and lower dopant concentrations did not show antibacterial activity.  相似文献   

16.
Time-of-flight secondary ion mass spectrometry (TOF-SIMS) was used for an in situ thermal decomposition study of Zn(CH3COO)2·2H2O forming ZnO nanoparticles. TOF-SIMS spectra were recorded at regular temperature intervals of 25 °C in positive and negative detection modes in a dynamic thermal process. Controlled heating (5 °C min−1) of Zn(CH3COO)2·2H2O was also carried out using thermogravimetric analysis (TGA) in an oxygen atmosphere (20 ml min−1). Nearly spherical ZnO nanoparticles with no agglomeration and a narrow size distribution (diameter ∼50 nm) were observed, which were characterized using scanning electron microscopy, transmission electron microscopy and x-ray diffraction. In situ thermo-TOF-SIMS was used to monitor the 64Zn+ and 66Zn+ ion abundances as a function of temperature, which showed a similar profile to that observed for weight loss in TGA during decomposition. Based on the experimental results, a possible decomposition mechanism for the formation of ZnO is proposed. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

17.
New zinc(II) and mercury(II) complexes of 2,2′-diamino-4,4′-bis(1,3-thiazole) (DABTZ), [M(DABTZ)(CH3COO)2], have been synthesized and characterized by elemental analysis, IR-, 1H NMR-, 13C NMR spectroscopy and studied by thermal analysis and X-ray crystallography. The structural characterization of the [Zn(DABTZ)(CH3COO)2] complex shows the complex to be a monomer and the Zn coordinated by two nitrogen atoms of the “DABTZ” ligand and four oxygen atoms of the acetate anions.  相似文献   

18.
Three linear trinuclear Schiff base complexes, {Zn[Zn(CH3COO)(C17H16N2O2)]2} ( 1 ), {Zn[Zn(CH3COO)(C25H20N2O2)]2} ( 2 ), and {Cd[Cd(CH3COO)(C18H18N2O2)]2} ( 3 ), were synthesized for the first time under solvolthermal conditions. Their structures have been characterized by elemental analyses, X-ray single crystal determinations, and infrared spectroscopy. There are three bridges across the M-M atom pairs (M is Zn for 1 and 2 , or Cd for 3 ) in each complex, involving two O atoms of a Schiff base ligand (N,N′-bis(salicylidene)-1, 3-propanediaminate (SALPD2-) for 1 , N, N′-bis(2-hydroxy-naphthalmethenylimino)-1, 3-propanediaminate (NAPTPD2-) for 2 , and N,N′-bis-(salicylidene)-1,4-butanediaminate (SALBD2-) for 3 ), and an O-C-O moiety of a μ-acetato group. In each of the complexes, the central M2+ ion is located on an inversion center and has a distorted octahedral coordination involving four bridging O atoms from two Schiff base ligands in the equatorial plane and one O atom from each bridging acetate group in the axial positions. The coordination around the terminal M2+ ions is irregular square pyramidal, with two O atoms and two N atoms of the Schiff base ligand in the basal plane and one O atom from an acetate group in the apical position. The acetate bridges linking the central and terminal M2+ ions are mutually trans. The M…M distances are 3.050(3) Å in 1 , 3.139(2) Å in 2 , and 3.287(6) Å in 3 .  相似文献   

19.
Nanoparticles of a Zn(II) coordination polymer {[Zn(DADMBTZ)(CH3COO)2] n , DADMBTZ?=?2,2′-diamino-5,5′-dimethyl-4,4′-bithiazole} were synthesized by reaction of Zn(NO3)2?·?4H2O, CH3COONH4 and DADMBTZ by a sonochemical method. The nanoparticles were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and Fourier transform infrared (FT-IR) spectroscopy. [Zn(DADMBTZ)(CH3COO)2] n was structurally characterized by single-crystal X-ray diffraction. In this four-coordinate compound with nearly C2 symmetry, DADMBTZ is bidentate. The metal lies in a pseudo-tetrahedral environment and is ligated by the two bithiazole ring nitrogen atoms and an oxygen from each of the two monodentate acetates; 2-D networks are formed via N–H···O hydrogen bonds. Thermal stability of [Zn(DADMBTZ)(CH3COO)2] n was studied by thermal gravimetric and differential thermal analyses. A ZnO nanostructure was obtained by direct thermolyses at 500°C under air. The ZnO nanostructure was characterized by SEM, XRD, and FT-IR spectroscopy.  相似文献   

20.
Zinc(II) complexes with 1,10-phenanthroline (phen) and 2,2′-bipyridine (bpy) containing two different anions have been synthesized and characterized by elemental analysis, IR-, 1H?NMR-, 13C?NMR spectroscopy. The single crystal X-ray data of [Zn(phen)2(CCl3COO)(H2O)](NO3) show the complex to be monomeric and the Zn atom with an unsymmetrical six-coordinate geometry, coordinated by four nitrogen atoms of “phen”, one trichloroacetate and one water. The crystal structure of [Zn(bpy)2(CH3COO)](ClO4)?·?H2O shows each zinc atom chelated by the nitrogen atoms of “bpy” and also two oxygen atoms of acetate. From the infrared spectra and X-ray crystallography, it is established that coordination of the carboxylate group to zinc is different for trichloroacetate and acetate.  相似文献   

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