共查询到19条相似文献,搜索用时 156 毫秒
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使用柔性含S有机配体4-(2-噻吩-2-基-乙基)-4H-[1,2,4]三氮唑(L),通过调控反应参数成功制备出4个基于Keggin的化合物,即[Cu3ⅠL3(PMo12O40)](1)、[Cu4ⅠL6(SiW12O40)](2)、[Cu4ⅠL6(SiMo12O40)](3)和[Zn4L6(SiW12O40)](4),并利用单晶X射线衍射、元素分析和红外光谱进行表征。化合物1中3个Cu+离子聚合3个配体诱导一个环状的三核铜簇。Keggin多阴离子连接三核簇构筑二维层结构。化合物2、3和4同构,包含由6个配体连接4个金属离子(2、3中为铜离子,4中为锌离子)形成的四核[M4L6]4+簇。多酸阴离子提供2个氧原子连接2个[M4L6]4+簇,从而形成一维链结构。标题化合物对废水中的阳离子染料亚甲基蓝(MB)展示了良好的选择性光催化性能。另外2-CPE(碳糊电极)可作为安培传感器来检测过氧化氢和亚硝酸根。化合物1、2和4展示了对Hg2+的传感性能。 相似文献
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以三(3,5-二甲基吡唑甲基)胺(TMPzA)及2,5-噻吩二羧酸为配体合成了2个双核Cu的配合物[Cu2(DMPzA)2(TPDC)2]ClO4(1)和[Cu2(TMPzA)2(TPDC)(H2O)2](ClO4)2(2)。在1中,配体TMPzA发生裂解,以二(3,5-二甲基吡唑甲基)胺(DMPzA)与Cu配位,并在2个Cu原子之间形成一个大环,2个Cu原子之间的距离为0.78684 nm。清除自由基实验发现,配合物1比2具有较好的清除自由基活性。 相似文献
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以三(3,5-二甲基吡唑甲基)胺(TMPzA)及2,5-噻吩二羧酸为配体合成了2个双核Cu的配合物[Cu2(DMPzA)2(TPDC)2]ClO4 (1)和 [Cu2(TMPzA)2(TPDC)(H2O)2](ClO4)2 (2)。在1中,配体TMPzA发生裂解,以二(3,5-二甲基吡唑甲基)胺(DMPzA)与Cu配位,并在2个Cu原子之间形成一个大环,2个Cu原子之间的距离为0.786 84 nm。清除自由基实验发现,配合物1比2具有较好的清除自由基活性。 相似文献
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摘要: 以优化的两步一锅反应法合成了生物金属有机化合物Fe(C5H4-CH2-Trp-OMe)2(FcL),通过NMR、HRMS及IR等对其结构进行了表征,利用X射线单晶衍射测定了分子结构。循环伏安法研究表明FcL在0.00~0.90 V电位范围内,给出一稳定的、形态良好的氧化还原峰,这归于化合物中Fc/Fc+电对的氧化还原过程。电化学金属离子识别研究显示FcL在过渡金属离子Zn2+和Cu2+的存在下,导致了配体Fc/Fc+式量电位的显著阳极移动,其△E0''对Zn2+和Cu2+分别为342和335 mV,表明了FcL对Zn2+和Cu2+具有良好的识别能力。 相似文献
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以3,5-二甲(丙)基-4-氨基-1,2,4-三唑为配体,与CuI在H2O/MeCN混合溶剂热合成了2个构型不同的Cu4I4超分子化合物{[Cu2(aadmtrz) I2]·CH3CN}n(1)和[Cu2(dptrz) I]n(2)(aadmtrz=4-((1-氨乙基)-氨基)-3,5-二甲基-1,2,4-三唑,dptrz=3,5-二丙基-1,2,4-三唑),并进行了元素分析,红外,X射线粉末衍射及单晶衍射等表征。2个配合物中Cu4I4构型不同,配合物1中,Cu4I4簇连结成一个8环椅式-椅式结构,通过配体连接成(4,4)二维菱形格子结构;而配合物2中,Cu4I4簇呈畸变的立方烷结构,构成了含有19.5%孔隙率三维孔洞聚合物,其结构可简化为(3,4)-连接的拓朴结构。同时,在常温下研究了2个配合物的固体荧光性质。 相似文献
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以3,5-二甲(丙)基-4-氨基-1,2,4-三唑为配体,与CuI在H2O/MeCN混合溶剂热合成了2个构型不同的Cu4I4超分子化合物{[Cu2(aadmtrz)I2]·CH3CN}n (1)和[Cu2(dptrz)I]n (2)(aadmtrz=4-((1-氨乙基)-氨基)-3,5-二甲基-1,2,4-三唑,dptrz=3,5-二丙基-1,2,4-三唑),并进行了元素分析,红外,X射线粉末衍射及单晶衍射等表征。2个配合物中Cu4I4构型不同,配合物1中,Cu4I4簇连结成一个8环椅式-椅式结构,通过配体连接成(4,4)二维菱形格子结构;而配合物2中,Cu4I4簇呈畸变的立方烷结构,构成了含有19.5%孔隙率三维孔洞聚合物,其结构可简化为(3,4)-连接的拓朴结构。同时,在常温下研究了2个配合物的固体荧光性质。 相似文献
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分别以3-甲基-2-氨基吡啶(L1)、5-溴-2-氨基吡啶(L2)为配体,采用溶液法合成了2个新的双核铜配合物:[Cu2(CH3COO)4(L1)2](1)和[Cu2(CH3COO)4(L2)2](2),并利用熔点、红外光谱、紫外可见光谱、荧光光谱、高分辨质谱和X射线单晶衍射等手段对其进行表征。1属于正交晶系Pbca空间群; 2属于单斜晶系P21/n空间群。每个配合物含有2个铜中心离子、4个醋酸根离子和2个配体(L1或L2)分子;每个醋酸根都起到桥联作用,分别与2个Cu2+配位,形成笼状结构;每个Cu2+均为五配位变形四方锥构型。1和2对金黄色葡萄球菌、枯草芽孢杆菌、大肠杆菌显示出良好抑制作用;对DPPH·具有良好清除效果;均表现出准可逆氧化还原的电化学特性。 相似文献
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原位羟基化2,2′-联吡啶类配体及其新颖的铜(Ⅰ)和混价铜(Ⅰ,Ⅱ)超分子构筑的合成(英) 总被引:2,自引:0,他引:2
本文利用水热法合成了两个新型一价铜配合物[Cu2(ophen)2]·H2O的类同质多晶结构(1α和1β)和一个混合价的铜配合物[Cu2(obpy)2(NO3)]·H2O (2)。晶体结构分析表明:1α显现出于无水的类似物[Cu2(ophen)2]相同的堆积方式,1β则形成出新奇的空间堆积。混合价化合物2是完全离域的,通过氢键集聚体[(H2O)2(NO3-)2]将两个[Cu2(obpy)2]+单元连接起来形成哑铃状的四核结构。 相似文献
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用模板法合成了1个大环金属铜(II)配合物[CuLCl2]·3H2O
(1)和3个大环金属镍(II)配合物[NiLCl2] (2),[NiL](ClO4)2
(3)和[NiLH2](ClO4)4 (4)(L=3,10-二乙基-1,3,5,8,10,12-六氮杂十四烷),通过X-射线衍射单晶结构分析测定了它们的晶体结构。晶体结构显示:配合物1和2的金属离子与大环配体的4个氮原子及大环平面轴向的2个氯离子以八面体配位方式配位;配合物3和4的金属离子与大环配体的4个氮原子以平面正方形配位方式配位,配合物4的侧链氮原子的质子化导致侧链结构翻转,使得其侧链与大环平面共面。 相似文献
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Masami Yonemura Yuuki Nakamura Naoki Usuki Hisashi kawa 《Journal of Chemical Sciences》2000,112(3):291-310
This paper discusses coordination-position isomeric MIICuII and CuIIMII complexes, using unsymmetric dinucleating macrocycles (Lm;n)2− ((L2;2)2−, (L2;3)2− and (L2;4)2−) that comprise two 2-(N-methyl)-aminomethyl-6-iminomethyl-4-bromo-phenonate entities, combined through the ethylene chain
(m = 2) between the two amine nitrogens and through the ethylene, trimethylene or tetramethylene chain(n = 2, 3 or 4) between the two imine nitrogens. The macrocycles have dissimilar N(amine)2O2 and N(imine)2O2 metal-binding sites sharing the phenolic oxygens. The reaction of the mononuclear CuII precursors, [Cu(L2;2)], [Cu(L2;2)] and [Cu(L2;2)], with a MII perchlorate and a MII acetate salt formed (acetato)MIICuII complexes: [CoCu(L2;2)(AcO)]ClO4·0.5H2O] (1), [NiCu(L2;2) (AcO)]ClO4 (2), [ZnCu(L2;2) (AcO)]ClO4 (3), [CoCu(L2;3)(AcO)]ClO4·0.5H2O (4), [NiCu(L2;3)(AcO)]ClO4 (5), [ZnCu(L2;3)(AcO)]ClO4·0.5H2O (6), [CoCu(L2;4)(AcO)(DMF)]ClO4 (7), [NiCu(L2;4) (AcO)]ClO4·2DMF (8) and [ZnCu(L2;4)(AcO)]ClO4 (9) (the formulation [MaMb (Lm;n)]2+ means that Ma resides in the aminic site and Mb in the iminic site). The site selectivity of the metal ions is demonstrated by X-ray crystallographic studies for 2·MeOH,3,5,7, and9. An (acetato)CuIIZnII complex, [CuZn(L2;3)(AcO)]ClO4 (10), was obtained by the reaction of [PbCu(L2;3)]-(ClO4)2 with ZnSO4·4H2O, in the presence of sodium acetate. Other complexes of the CuIIMII type were thermodynamically unstable to cause a scrambling of metal ions. The Cu migration from the iminic site to the aminic
site in the synthesis of10 is explained by the ‘kinetic macrocyclic effect’. The coordination-position isomers,6 and10, are differentiated by physicochemical properties. 相似文献
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《Journal of Coordination Chemistry》2012,65(11):1997-2005
The DNA cleavage activities of two coordination polymers of Robson-type macrocycles, {[Cu4L1(4,4′-bipy)2](ClO4)4·H2O}∞ (1) and {[Cu4L2(4,4′-bipy)4](ClO4)4·2CH3CN·2H2O}∞ (2) (where H2L1 and H2L2 are the [2 + 2] condensation products of 1,3-diaminopropane with 2,6-diformyl-4-methylphenol and 2,6-diformyl-4-fluorophenol, respectively), have been studied. The interactions of the complexes with calf thymus-DNA were investigated by UV–vis spectroscopy, CD spectroscopy, and gel electrophoresis. The binding constants of 1 and 2 are 7.2 × 104 and 2.1 × 105 M?1, respectively. The complexes exhibit DNA cleavage activity, with the cleavage process involving oxidative cleavage of DNA. 相似文献
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V. A. Igonin S. V. Lindeman Yu. T. Struchkov Yu. A. Molodtsova O. I. Shchegolikhina A. A. Zhdanov 《Russian Chemical Bulletin》1993,42(4):718-722
The structure of K2{[EtSiO2]6K2Cu4[O2SiEt]6} · 4n-BuOH, a novel mixed sandwich-like complex of K+ and Cu2+ with two 6-membered macrocyclic ethylsiloxanolate ligands, was established by means of X-ray study. The ligands have an all-cis configuration and a crown conformation. Four Cu2+ and two K+ ions form a planar hexagon sandwiched between antiparallel coaxial macrocyclic ligands. The K+ ions occupy two opposite apices of the hexagon. The Cu2+ ions have square-planar coordination with four siloxanolate OM atoms, while the K+ ions, are coordinated with two O atoms of the solvating butanol molecules, in addition to four OM atoms. The electric neutrality of the whole complex is due to the two outer-sphere K+ counter-ions, each located over one of the two siloxanolate macrocycles, i.e., over the «decks» of the sandwich and coordinated with endocyclic siloxane OSi atoms, as in crown-ether complexes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 752–756, April, 1993. 相似文献
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The autoxidation of the Cu+ complexes with a series of six 12-, 14- and 16-membered macrocycles containing the N2S2 set of donor atoms has been studied with an oxygen electrode and with the stopped-flow technique. Inspite of the identical set of coordinating groups, the reactivity of the Cu= complexes towards O2 varies by more than 5 orders of magnitude, with rate constants between <0.1 and 2·104 M?1S?1. Simple bimolecular rate laws are obtained from initial rates of autoxidation, but successive one-electron transfers with intermediate formation of superoxide are implied from the analysis of complete reaction curves for complexes with the 12-membered macrocycles. The kinetic parameters are compared with the redox potentials for the corresponding CuL2+/CuL+ couples. Only a rather rough correlation is found and steric factors must in addition be responsible for the observed reactivity pattern which shows a decrease of autoxidation rate with increasing size of the macrocyclic ring. No systematic effect was observed for the influence of cis- vs. trans-configuration of the donor atoms. 相似文献
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Hakan Alp Zekeriya Biyiklioğlu Gülsev Dilber ÜmmÜhan Ocak Aysel Marap Halit Kantekin 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(3-4):283-288
Synthetic procedures for new N2S4- and N2S5-donor macrocycles (2 and 4) were given. The ligands were prepared by the reaction of NaBH4 with the appropriate macrocyclic diamide in the presence of boron trifluoride ethyl etherate in dry tetrahydrofuran (THF).
Solvent extraction method was used to evaluate metal-ion binding properties of the new ligands. The solvent extraction experiments
suggested that the reduced macrocycles have Ag+ and Hg2+ selectivities compared to Pb2+, Co2+, Zn2+, Ni2+, Cu2+, Mn2+ and Cd2+ ions. The extraction constants (log K
ex) and complex compositions were determined for Ag+ and Hg2+ complex of compound (4). 相似文献
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Summary The polarographic reduction at a dropping mercury electrode of several CuII, NiII and CoIII complexes of tetraaza macrocycles has been studied in 0.1M NaClO4 as supporting electrolyte. The CuII complexes show values of half-wave potentials which can be correlated to the ring size and ligand field stabilisation. A similar, though less marked, trend is noticeable in the reduction of the NiII complexes. No such conclusions can be drawn in the case of the CoIII complexes. 相似文献
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The synthesis is described of four new chiral liquid crystalline monomers (M2–M5 ) and their corresponding side‐chain homopolysiloxanes (P2–P5 ) containing menthyl groups. Chemical structures were characterised using FT‐IR or 1H NMR spectra, and specific optical rotations were evaluated with a polarimeter. The phase behaviour and mesomorphic properties of the new compounds were investigated by differential scanning calorimetry, thermogravimetric analysis, polarising optical microscopy, UV/visible/NIR spectrocopy and X‐ray diffraction. The monomers and homopolymers with more aryl segments showed noticeably lower specific optical rotation value. The monomers M2–M5 formed a cholesteric or blue phase when a flexible spacer was inserted between the rigid mesogenic core and the terminal menthyl groups by reducing the steric effect. M2–M5 revealed enantiotropic cholesteric phase. Moreover, M2 also exhibited a monotropic smectic A (SmA) phase, and M4 also exhibited a cubic blue phase on cooling. The selective reflection of light shifted to the long wavelength region with increasing rigidity of the mesogenic core for M2–M5 . P2–P5 exhibited SmA phases, and the mesogenic moieties were ordered in smectic orientation with their centres of gravity in planes. Melting or glass transition temperature and the clearing temperature increased, and the mesophase temperature range widened with increasing rigidity of the mesogenic core. 相似文献
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《Journal of Coordination Chemistry》2012,65(23):4131-4143
Two copper(II) complexes, [Cu2(μ-benzoato)(L1)2]NO3·2H2O (1) and [Cu2(μ-succinato)(L2)2(H2O)]ClO4 (2), have been synthesized, where L1 = N′-[(E)-phenyl(pyridin-2-yl)methylidene]benzoylhydrazone and L2 = N′-[(E)-pyridin-2-ylmethylidene]benzoylhydrazone. These complexes were characterized including by single-crystal X-ray diffraction studies. The copper is five-coordinate in 1 while in 2 one copper is five-coordinate and the other is six-coordinate. Electrochemical behavior of these complexes was measured by cyclic voltammetry. The conproportionation equilibrium constants (Kcon) for both complexes have been estimated. The superoxide dismutase (SOD) activities of 1 and 2 were measured by nitro blue tetrazolium assay. Complex 1 has better SOD activity than 2. 相似文献