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将过渡金属配合物阳离子([M(DETA)2]n+(M=Cu2+,Ni2+,Co3+;DETA=Diethylenetriamine,二乙烯三胺)作为客体插入层状MnPS3层间得到了相应的3个夹层化合物。通过X-射线粉末衍射、元素分析和红外光谱对夹层化合物的结构进行了表征。结果表明,与主体MnPS3 0.65 nm的层间距相比较,夹层化合物(Mn0.88PS3[Cu(DETA)2]0.12)的层间距扩大了0.32 nm,由此推测客体[Cu(DETA)2]2+在层间以平面四方的配位形式存在,而另2个夹层化合物(Mn0.79PS3[Ni(DETA)2]0.21和Mn0.74PS3[Co(DETA)2]0.17)的层间距扩大了0.48 nm,说明客体[(M(DETA)2]n+,M=Co3+,Ni2+) 在主体层间以八面体配位形式存在。磁性测试结果表明过渡金属离子[(M(DETA)2]n+(M=Cu2+,Co3+)的插入能引起主体MnPS3的磁性在35~40 K发生由顺磁向亚铁磁性的转变并表现自发磁化,而客体[Ni(DETA)2]2+却使夹层化合物的反铁磁相互作用增强,抑制了自发磁化的发生。 相似文献
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大脑中淀粉样Cross-β纤维沉淀是老年痴呆症(AD)的一个关键性病理特征. X射线分析显示有大量Cu2+和Zn2+集中到患者的大脑中, 暗示了这些失调的离子与AD疾病有关. 实验发现, 在适度酸性pH值下, Cu2+与组氨酸咪唑环上的Nt配位可诱导Ab多肽聚合成沉淀, 而在中性pH值下, Cu2+与组氨酸咪唑环上的Np及主链上的去质子N或O配位生成可溶的配位化合物. 本文应用密度泛函理论(B3LYP)方法, 研究了Cu2+与Ab多肽中的四肽(HHQK)形成可溶性配合物的结构, 结果得到N(3)O(1)及N(4)O(1)两类配位方式, 其中以N(3)O(1)配位形成变形的平面正方形配位结构, 而以N(4)O(1)配位形成变形的四方锥结构. 由于分子内氢键的形成, 优化得到了6个不同的结构, 通过能量对比找到了最稳定的结构, 并深入探讨了最稳定结构的原子电荷布居规律、一些前沿分子轨道以及配合物的振动光谱, 在振动光谱方面, 理论与实验符合得很好. 相似文献
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有机化合物因成膜以后荧光淬灭而使其应用受到很大限制, 所以研究、开发能在聚集状态下呈现优异发光性能的新材料就尤为重要. 由于分子间π-π和极性共同相互作用, 使得磷酰杂菲环的转动受到限制, 从而使苯甲酸-2-[6-氧化-6-氢-二苯基(c,e)<1,2>氧杂磷酰基]-1,4-二羟基苯二酯(OP)在达到一定规整聚集程度时, 荧光强度成倍增加, 具有了聚集诱导发光增强(AIEE)性质. 实验结果表明: 浓度低于1×10-6 mol•L-1 的OP会失去AIEE性质; 浓度为1×10-4 mol•L-1的Hg2+, Fe2+和 Fe3+会分别淬灭浓度为1×10-5 mol•L-1 OP荧光强度的26%, 34%, 74%, 而Pb2+, Zn2+, Cd2+, Co2+, Mn2+, Cu2+, Ni2+, Ag+等离子的淬灭效率却很低, 这一性质表明该化合物可以用作过渡金属离子的特异性检测材料. 相似文献
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通过自组装得到一种具有适中配位键强度和适度骨架柔性的二维Cd基金属有机骨架(MOF){[Cd (HL)(BPY)0.5(H2O)]·2H2O}n (1),其中H3L=4,4'',4″-(亚硝基三(亚甲基))三苯甲酸,BPY=4,4''-联吡啶)。由于其独特的结构特征,在金属离子(Zn2+/Ni2+/Co2+)刺激下,1逐渐转变成相应金属离子主导的MOF结构2、3和4。在此过程中,随着金属离子Cd2+→Zn2+、Cd2+→Ni2+和Cd2+→Co2+的交换,1通道中自由的Cd2+和L3-与MOF的骨架进行融合,导致通道空间的扩大,发生次级构筑单元(SBU)的转变,进而形成可调节的骨架。光催化二氧化碳还原结果表明,由离子交换所得到的新结构在催化效率上并没有很大改观,但在产物选择性上却有极大地提升(其中配合物3展示出100%的CO选择性)。 相似文献
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用分光光度法研究了2.6-二乙酰基吡啶缩二(氨基疏脲)与 Cu2+,Co2+,Ni2+,Zn2+的配位反应,用作图法和自编的LEMIT-S程序计算了配合物的组成,摩尔吸光系数和稳定常数,两法所得的结果基本一致,结果表明,在乙醇中Cu2+与配体daptsc形成Cu2(daptsc)和Cu(daptsc),二者在溶液中共存,而Cu2+在DMF中仅生成1:1配合物,其它金属离子在两种溶剂中均形成1:1型。在两种溶剂中lgβ11的顺序为:Zn > Cu > Ni > Co. 相似文献
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A new dioxime ligand, N,N-bis(2-{[(2,2-dimethyl-1,3-dioxolan-4-yl)methyl]amino} ethyl)N′,N′-dihydroxyethanediimidamide (H2L), and its mononuclear complexes with Co2+, Ni2+, Cu2+, Zn2+ and Cd2+ are synthesized. H2L forms transition metal complexes [Co(LH)2(H2O)2] and [M(LH)2] (M = Ni2+, Cu2+) with a metal : ligand ratio of 1 : 2. Complexes [M(H2L)(Cl)2] (Zn2+, Cd2+) have a metal : ligand ratio of 1 : 1. The mononuclear Co2+, Ni2+, and Cu2+ complexes indicate that the metal ions coordinate ligand through its two N atoms, as the most of dioximes. In the Co2+ complex, two water molecules and in the Zn2+ and Cd2+ complexes two chloride ions are also coordinated to the metal ion. The structures of these compounds are identified by elemental analyses, IR, 1H and 13C NMR, electronic spectra, magnetic susceptibility measurements, conductivity, and thermogravimetric analysis.__________From Koordinatsionnaya Khimiya, Vol. 31, No. 7, 2005, pp. 540–544.Original English Text Copyright © 2005 by Canpolat, Kaya.The text was submitted by the authors in English. 相似文献
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Jos Terheijden Willem L. Driessen Willem L. Groeneveld 《Transition Metal Chemistry》1980,5(1):346-350
Summary Several new coordination compounds are reported withN-carbamoylpyrazole (Hcpz) as the ligand;viz. M(cpz)2 where M = CuII and NiII; M(Hcpz)Cl2 where M = MnII, CoII, CuII, ZnII and CdII; M(Hcpz)2Cl2 Where M = FeII, CoII and NiII: M(Hcpz)3(BF4)2 where M = FeII, CoII, NiII, ZnII and CdII; and Cu(Hcpz)2(BF4)2. In the salts, Hcpz is coordinated through the nitrogen atoms of the pyrazole ring and the nitrogen atom of the carbamoyl group. In the Hcpz complexes, coordination takes place through the nitrogen atom of the pyrazole ring and the oxygen atom of the carbamoyl group. 相似文献
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Complexes of N-phthaloylglycinate (N-phthgly) and CoII, NiII, CuII, ZnII and CdII containing imidazole (imi), N-methylimidazole (mimi), 2,2-bipyridyl (bipy) and 1,10-phenanthroline (phen), and tridentate amines such as 2,2,2-terpyridine (terpy) and 2,4,6-(2-pyridyl)s-triazine (tptz), were prepared and characterized by conventional methods, i.r. spectra and by thermogravimetric analysis. For imi and mimi ternary complexes, the general formula [M(imi/mimi)2(N-phthgly)2]·nH2O, where M = CoII, NiII, CuII and ZnII applies. For CdII ternary complexes with imi, [Cd(imi)3(N-phthgly)2]·2H2O applies. For the bi and tridentate ligands, ternary complexes of the formula [M(L)(N-phthgly)2]·nH2O were obtained, where M = CoII, NiII, CuII and ZnII; L = bipy, phen, tptz and terpy. In all complexes, N-phthgly acts as a monodentate ligand, coordinating metal ions through the carboxylate oxygen, except for the ternary complexes of CoII, NiII and CuII with mimi and CuII and ZnII with imi, where the N-phthgly acts as a bidentate ligand, coordinating the metal ions through both carboxylate oxygen atoms. 相似文献
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《Journal of Coordination Chemistry》2012,65(10):875-882
CoII, NiII, CuII, ZnII and CdII complexes of N,N-bis(2-{[(2-methyl-2-phenyl-1,3-dioxolan-4-yl)methyl]amino}butyl)N′,N′-dihydroxyethanediimidamide (LH2) were synthesized and characterized by elemental analyses, IR, 1H- and 13C-NMR spectra, electronic spectra, magnetic susceptibility measurements, conductivity measurements and thermogravimetric analyses (TGA). The CoII, NiII and CuII complexes of LH2 were synthesized with 1?:?2 metal ligand stoichiometry. ZnII and CdII complexes with LH2 have a metal ligand ratio of 1?:?1. The reaction of LH2 with CoII, NiII, CuII, ZnII and CdII chloride give complexes Ni(LH)2, Cu(LH)2, Zn(LH2)(Cl)2, Cd(LH2)(Cl)2, respectively. 相似文献
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Offiong E. Offiong 《Transition Metal Chemistry》1995,20(2):126-131
Summary The stereochemistry and complexation behaviour of diphenyl diketone monothiosemicarbazone (DKTS) with CuII, CoII, NiII, CdII, ZnII, PdII, PtII, RuIII, RhIII and IrIII have been investigated by means of chemical, magnetic and spectral (i.r., Raman, 1H- and 13C-n.m.r. and electronic) studies. The ligand forms complexes of the M(DKTS)2 type with NiII, CuII and CoII having a distorted octahedral geometry. The absence of a v(M—X) band in the i.r. spectra, coupled with their 1:1 electrolytic conductances, suggests that RuIII, RhIII and IrIII form octahedral complexes of the [M(DKTS)2]Cl type. A four-coordinate structure involving bridging halides is proposed for the ZnII, CdII, PdII and PtII complexes, which have relatively low v(M—X) vibration modes. 相似文献
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The complex formation by Co2+, Ni2+, Cu2+, Zn2+, and Cd2+ with tris[2-(dimethylamino)ethyl]amine (N(CH2CH2NMe2)3, Me6tren) was investigated at 25° and at an ionic strength of 1, using VIS spectroscopy and potentiometric measurements. The stability constants of these complexes are compared with those of tris(2-aminoethyl)amine (N(CH2CH2NH2)3, tren), obtained under the same conditions. The values of the constants for Me6tren are much lower than those for tren, due to the bulky Me substituents. The values of the constants can be correlated with the ability of the individual metal ions to adopt coordination number 5. This appears to be easier for Cu2+ and Co2+ than for Cd2+ and Zn2+ and is very difficult for Ni2+. The 1:1 complexes [ML(H2O)]2+ are monoprotonic acids whose pKs values are similar or lower than those of the corresponding aquametal ions. The X-ray crystal structure of the copper(II) complex [Cu(SO4)(Me6tren)] · 8H2O reveals pentacoordination at the central ion. The UV/VIS spectra of the aqueous solutions of the Co2+, Ni2+, and Cu2+ 1:1 complexes confirm that the same coordination number is present also in these complexes. 相似文献
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Mohammad Akbar Ali Kalugamage Rodney Fernando Debasish Palit Mohamed Nazimuddin 《Transition Metal Chemistry》1995,20(1):19-22
Summary New complexes of general formulae [Ni(HL)2], [ML]·H2O and [Cu(HL)X] (H2L = pyrrole-2-aldehyde Schiff bases ofS-methyl- andS-benzyldithiocarbazates; X = Cl or Br; M = NiII, CuII, ZnII or CdII) were prepared and characterized by a variety of physicochemical techniques. The Schiff bases coordinate as NS bidentate chelating agents in [Ni(HL)2] and [Cu(HL)X], and as tridentate NNS chelates in [ML] (M = NiII, CuII, ZnII or CdII). Both the [Ni(HL)2] and [NiL] complexes are diamagnetic and square-planar. Based on magnetic and spectroscopic evidence, thiolate sulphur-bridged dimeric square-planar structures are assigned to the [Cu(HL)X] and [ML] (M = NiII or CuII) complexes. The complexes ML (M = ZnII or CdII) are polymeric and octahedral. 相似文献
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The interactions of ciprofloxacin (HCipro) with transition metals have been investigated. Two types of complexes, [M(Cipro)(OAc)(H2O)2] · 3H2O (M = MnII, CoII, CuII or CdII) and [M(Cipro)(OAc)] · 6H2O (M = NiII or ZnII), were obtained and characterized by physicochemical and spectroscopic methods. The i.r. spectra of the complexes suggest that the ciprofloxacin behaves as a monoanionic bidentate ligand. In vitro antibacterial activities of the HCipro and the complexes were tested. 相似文献
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Boyapati Venkateswara Rao Neelam Palta Surendra N. Dubey Desh M. Puri 《Transition Metal Chemistry》1985,10(2):60-62
Summary Ethylene- ando-phenylene-diamine-N, N-bis(dimethylmethylenephosphonic) acids form polymeric complexes of general formula M2L · xH2O (M = MnII, CoII, NiII, CuII, ZnII, CdII or PbII; x=2 or 4). These have octahedral geometry and are polymeric, according to i.r. (far and near) and electronic spectral data and magnetic moment and thermogravimetric studies. The ligands are thought to be tetradentate for each metal atom, coordination taking place through phosphoryl oxygen and amino-group nitrogen. 相似文献
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Summary Complexes of 4-(2-thiazolyl)-1-(2,6-diacetylpyridine)-thiosemicarbazone, H2C3NSCNH(S)NHNCMeC5H3N-C(O)Me (Htdaptsc) of the compositions [M(Htdaptsc)2Cl2] [M=MnII, CoII, NiII or ZnII] [M(Htdaptsc)Cl2] [M=ZnII, CdII or HgII] and [M(tdaptsc)2] [M=MnII, CoII, NiII, CuII, or ZnII] have been prepared and characterized by elemental analyses, molar conductance, magnetic susceptibility, electronic, e.s.r. and i.r. studies, and their stereochemistries are discussed. 相似文献