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1.
The reactions of transition metal macrocyclic complexes [ML](ClO4)2 (L?=?5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, M?=?Ni, Cu) with NH4VO3 under hydrothermal conditions gave two coordination polymers, namely [NiL]2[V6O17] and [CuL]2[V6O17]. Single-crystal X-ray diffraction analyses indicated that the central Ni(II)/Cu(II) atom displays a distorted six-coordinate octahedral coordination geometry by coordination with four nitrogen atoms of L, and two oxygen atoms of [VO4] tetrahedrons. Compounds [NiL]2[V6O17] and [CuL]2[V6O17] show three-dimensional structures, which are constructed through the connections of dodecanuclear [V12O32]4? rings with [NiL]2+ in [NiL]2[V6O17], and [V8O22] n 4n? chains with [CuL]2+ in [CuL]2[V6O17], respectively, generating one-dimensional channels. 相似文献
2.
Transition Metal Chemistry - In this research, four hybrid materials, namely [Ni(MC)]3[VO3]6·12.25H2O (1), [Cu(MC)]3[VO3]6 (2), [Ni(PC)]3[VO3]6·2H2O (3), and [Cu(PC)]3[VO3]6·2H2O (4)... 相似文献
3.
Three novel heteropolytungstates, [Cu(phen)2]4[α-SiW12O40] (1), [Cu4(4,4′-bpy)3(2,2′-bpy)4][α-SiW12O40] · H2O (2) and [Cu(4,4′-bpy)(4,4′-Hbpy)0.5]2[PW12O40] (3) (phen = 1,10-phenanthroline, 4,4′-bpy = 4,4′-bipyridine, 2,2′-bpy = 2,2′-bipyridine), have been synthesized and characterized
by elemental analyses, IR, TG analyses and single-crystal X-ray diffraction. Compound (1) exhibits interesting chiral layer constructed from interperpendicular helical chains running along a crystallographic 21 axis in the c and a directions. Furthermore, the chiral layers are connected by the [α-SiW12O40]4− anions via hydrogen bonding interactions to form a 3D superamolecular structure. The [Cu4(4,4′-bpy)3(2,2′-bpy)4]4+ coordinated complexes in compound (2) are packed together via the aromatic π–π stacking interactions and exhibit an interesting 3D sandglasslike “host” network with 1D channels, in which
[α-SiW12O40]4− anions “guests” reside. Compound (3) has a unique 2D superamolecular network, which is composed of cationic CuI coordination polymer chains and discrete [PW12O40]3− polyoxoanions as linkers. It is noteworthy that the monprotonated 4,4′-bpy ligands of (3) act as arms and connect the adjacent 2D network, generating a 3D interpenetrating superamolecular structure. 相似文献
4.
Three new azamacrocylic complexes of divalent transition-metal ions were synthesized by taking Co(II), Ni(II), and Cu(II) metal ions as templates. The macrocyclic ligand (12Z,52Z,54E)-11,12,13,14,15,16,51,52,53,54,55,56-dodecahydro-2,4,6,8-tetraaza-1 (2,4),5(4,2)-pyrimidine-3,7(1,2)-dibenzenacyclooctaphane-16,56-dione was derived from o-phenylenediamine (OPD) and 2-thiobarbituric acid (TBA). All the complexes were fully characterized through spectroscopic techniques and elemental analyses. The structures of the macrocyclic complexes were determined by IR, UV–vis, ESI-MS, TGA, molar conductance, magnetic moment, and electron spin resonance data. On the basis of the above studies, the complexes may be formulated as [MLX2], in which L is a macrocyclic ligand and X = CH3COO−. All the macrocyclic complexes were biologically screened to evaluate their antimicrobial efficacy. DNA binding study of two representative complexes was performed by UV–vis titrations. 相似文献
5.
《Journal of Coordination Chemistry》2012,65(17):3102-3109
Two new linear trinuclear complexes, [Co(NiL1)2(SCN)2] (1) and [Co(NiL2)2(H2O)2](ClO4)2?·?2C2H5OH (2), have been prepared by using Co(ClO4)2?·?6H2O and two macrocyclic complex ligands NiL1 and NiL2. L1 and L2 are the doubly deprotonated forms of dimethyl 5,6,7,8,15,16-hexahydro-6,7-dioxodibenzo[1,4,8,11]tetraazabicyclo[12.4.015,16]13,18-dicarboxylate and dimethyl 5,6,7,8,15,16-hexahydro-15-methyl-6,7-dioxodibenzo[1,4,8,11]tetraazacyclotetradecine-13,18-dicarboxylate, respectively. X-ray single crystal analyses reveal the coordination geometries around Ni(II) in both 1 and 2 are identical and slightly distorted square planar with N4 donors; all Ni–N bonds in the two complexes are very short. The Co(II) ions are at the centers of the trinuclear complexes and have distorted octahedral coordination geometries of O4N2 donors in 1 and an O6 in 2. π?···?π interactions involving aromatic and non-aromatic π-systems join the trinuclear entities to form 2-D layers in the crystals of 1 and 2. 相似文献
6.
M. L. Rojas-Cervantes B. Casal P. Aranda M. Savirón J. C. Galván E. Ruiz-Hitzky 《Colloid and polymer science》2001,279(10):990-1004
Neutral macrocyclic compounds (crown ethers and cryptands) and charged molecular species (alkylammonium iodides) were intercalated
into vanadium oxide xerogel (V2O5 · nH2O) to study their influence on the electrical behaviour of this inorganic 2D host lattice. Treatment with alkyl or arylammonium
iodide solutions produced the intercalation of organic cations accompanied by the reduction of a fraction of V (V) to V (IV).
Characterisation by different techniques allowed the postulation of the interlayer arrangement of the guest species. The study
of electrical behaviour at different temperatures indicated that the properties of the hybrid materials can be mainly related
to the nature of guest species, the degree of host lattice reduction, the interlayer water content, and the␣presence of metal
ions deliberately introduced in the system.
Received: 23 January 2001 Accepted: 5 April 2001 相似文献
7.
8.
《Journal of Coordination Chemistry》2012,65(8):1244-1252
Two one-dimensional linear coordination polymers, [Mg(L)?·?4(H2O)] (H2L?=?olsalazine) and 2 [Ca(L)?·?4(H2O)] were obtained from self-assembly of CaCl2 or MgSO4 with olsalazine and their structures determined by single crystal X-ray diffraction. Both complexes are one-dimensional polymers, for complex 1 with crystal data: P2(1)/c, a?=?9.5224(18), b?=?11.309(2), c?=?16.211(3)?Å, β?=?106.648(3)°, V?=?1672.6(6)?Å3, Z?=?4, R 1?=?0.0695, wR 2?=?0.2183, for complex 2 with crystal data: P4(3)2(1)2, a?=?10.4006(2), b?=?10.4006(2), c?=?32.0746(10)?Å, V?=?3469.59(14)?Å3, Z?=?8, R 1?=?0.0332, wR 2?=?0.1015. In the complexes, Mg and Ca adopt totally different coordination modes. Alkaline-earth Mg is six-coordinate octahedronal geometry, however, in 2, the local coordination geometry around calcium atom can be best described as a slightly distorted pentagonal bipyramid crystallizing in a homo-chiral space group. Olsalazine in both compounds also adopts dissimilar coordination modes. 相似文献
9.
合成了三个氰根桥联的十二核大环齿轮状配合物[Cr(bpmb)(CN)2]6-[Mn(5-Brsalpn)]6·12H2O(1)、[Co(bpmb)(CN)2]6[Mn(5-Brsalpn)]6·12H20(2)和[Co(bpmb)-(CN)2]6[Mn(5-Clsalpn)]6·24H20·8CH3CN(3)(bpmb^2-=1,2-bis(pyridine·2-carboxamido)-4-methylbenzenate),表征了其晶体结构和磁性.三配合物是同晶型的,包含交替排列的锰(Ⅲ)-Schiff碱阳离子和[M(bpmb)(CN)2]-阴离子,阴阳离子单元用氰根离子连成十二核环状结构.分子环直径约2nm.配合物1呈反铁磁性,说明通过氰根桥铬(Ⅲ).锰(Ⅲ)离子间存在反铁磁相互作用.基于一维交替链模型(哈密顿算符H=-JCrMnN∑i=0Si·Si+1)导出的磁化率公式与实验数据进行拟和得到磁耦合参数JCrMn=-2.65(6)cm^-1. 相似文献
10.
Three cyanide-bridged dodecanuclear macrocyclic wheel-like complexes [Cr(bpmb)(CN)2]6[Mn(5-Brsalpn)]6·12H2O (1), [Co(bpmb)(CN)2]6[Mn(5-Brsalpn)]6·12H2O (2) and [Co(bpmb)(CN)2]6[Mn(5-Clsalpn)]6·24H2O·8CH3CN (3) [bpmb2−= 1,2-bis(pyridine-2-carboxamido)-4-methylbenzenate dianion; 5-Brsalpn2− = N,N′-propylenebis(5-bromosalicylideneaminato) dianion; 5-Clsalpn2− = N,N′-propylenebis(5-chlorosalicylideneaminato) dianion] have been synthesized and their crystal structures and magnetic properties
have been investigated. The three compounds are structurally isomorphous and consist of alternating Mn(III)-Schiff base cations
and [M(bpmb)(CN)2]− anions, generating cyanide-bridged nanosized dodecanuclear macrocyclic structures with an approximate diameter of 2 nm. The
study of the magnetic properties of complex 1 reveals an antiferromagnetic interaction between the Cr(III) and Mn(III) ions
through the cyanide bridges. A best-fit to the magnetic susceptibility of the complex leads to a magnetic coupling constant
of J
CrMn = −2.65(6) cm−1 on the basis of a one-dimensional alternating chain model with the Hamiltonian $
H = - J_{CrMn} \sum\limits_{i = 0}^N {S_i \cdot S_{i + 1} }
$
H = - J_{CrMn} \sum\limits_{i = 0}^N {S_i \cdot S_{i + 1} }
. 相似文献
11.
A green and facile method was developed to prepare a novel hybrid nanocomposite that consisted of one-dimensional multi-walled carbon nanotubes (MWCNTs) and two-dimensional graphene oxide (GO) sheets. The as-prepared three-dimensional GO–MWCNTs hybrid nanocomposites exhibit excellent water-solubility owing to the high hydrophilicity of GO components; meanwhile, a certain amount of MWCNTs loaded on the surface of GO sheets through π–π interaction seem to be “dissolved” in water. Moreover, the graphene(G)-MWCNTs nanocomposites with excellent conductivity were obtained conveniently by the direct electrochemical reduction of GO–MWCNTs nanocomposites. Seeing that there is a good synergistic effect between MWCNTs and graphene components in enhancing preconcentration efficiency of metal ions and accelerating electron transfer rate at G-MWCNTs/electrolyte interface, the G-MWCNTs nanocomposites possess fast, simultaneous and sensitive detection performance for trace amounts of heavy metal ions. The electrochemical results demonstrate that the G-MWCNTs nanocomposites can act as a kind of practical sensing material to simultaneously determine Pb2+ and Cd2+ ions in terms of anodic stripping voltammetry (ASV). The linear calibration plots for Pb2+ and Cd2+ ranged from 0.5 μg L−1 to 30 μg L−1. The detection limits were determined to be 0.2 μg L−1 (S/N = 3) for Pb2+ and 0.1 μg L−1 (S/N = 3) for Cd2+ in the case of a deposition time of 180 s. It is worth mentioning that the G-MWCNTs modified electrodes were successfully applied to the simultaneous detection of Cd2+ and Pb2+ ions in real electroplating effluent samples containing lots of surface active impurities, showing a good application prospect in the determination of trace amounts of heavy metals. 相似文献
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13.
《Journal of Coordination Chemistry》2012,65(5):443-451
Two unsymmetrical, macrocyclic, heterodinuclear complexes, [CuIIMII(L)]?(ClO4)2·nH2O (n?=?3; M?=?Zn, Cd) have been obtained by cyclocondensation of N,N′-bis(3-formyl-5-n-butylsalicylidene)ethylenediimine and 1,3-diaminopropane in the presence of M2+. The structures of both complexes were determined by X-ray diffraction techniques. In each complex, two metals are located in the tetraimine macrocyclic cavity, and a water molecule and a perchlorate group are separately coordinated to the metal ions on the same side of the ring. Coordination geometry around each metal is approximately square pyramidal. ESMS spectra were used to characterize the complexes and isotopic distributions were investigated. 相似文献
14.
H. Xia X. Jiang L. Lin C. Jiang G. Liao 《Russian Journal of Coordination Chemistry》2013,39(12):896-901
Reaction of a macrocyclic copper(II) complex [Cu(L)](ClO4)2 · 3H2O (I) (L = 1,3,10,12,16,19-hexaazatetracyclotetracosane) with a hexapod carboxylate ligand H6TTHA (H6TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetic acid) and a tripod carboxylate ligand H3TATB (H3TATB = 4,4′,4″-S-triazine-2,4,6-triyl-tribenzoic acid) yielded two mononuclear copper(II) complexes [Cu(L)][H4TTHA] · 4H2O (II) and [Cu(L)][HTATB] · 4H2O (III). The complexes I–III have been structurally characterized. The crystal structures of complexes II and III show the copper(II) ion has a distorted pentacoordinate square-pyramidal geometry with two secondary and two tertiary amines from the macrocyclic complex [Cu(L)]2+ and one oxygen atom from the carboxylate ligand group at the axial position. The UV-Vis spectra are utilized to discuss the hydrolysis of the complex II. 相似文献
15.
D. P. Singh V. Malik R. Kumar K. Kumar J. Singh 《Russian Journal of Coordination Chemistry》2009,35(10):740-745
A new series of the macrocyclic complexes of type [M(C18H16N4O2)X2], where M = Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and X = Cl−, NO3−, CH3COO−, has been synthesized by the condensation of succinyldihydrazide with benzil in the presence of bivalent metal ions. The
complexes have been characterized with the aid of elemental analyses, conductance measurements, and electronic, NMR, and infrared
spectral studies. On the basis of these studies, a six-coordinate distorted octahedral geometry in which two nitrogen and
two carbonyl oxygen atoms are suitably placed for coordination toward metal ion has been proposed for all the complexes. The
complexes were tested for their in vitro antibacterial activity. Some of the complexes showed remarkable antibacterial activity
against some selected bacterial strains. 相似文献
16.
The reaction of VO(acac)2 with 2-benzoylpyridine substituted aroylhydrazones is studied. Oxovanadium(IV) and (V) complexes are obtained, indicating the binding of ligands to the metal ion through the imine nitrogen, enolate oxygen and pyridyl nitrogen. The oxovanadium(IV) compound [VOL1(OCH3)] · 0.14H2O (1a) gets oxidized to dioxovanadium(V) species [VO2L1] (1b) upon crystal formation. The crystal structures of the ligand and the two vanadium complexes are reported. Single crystal X-ray diffraction studies of the compound [VO(HL2)(μ2-O)]2 (2) revealed a centrosymmetric dimer. 相似文献
17.
Two symmetrical macrocyclic dinuclear complexes, [Cu2L1(ClO4)2(H2O)2][Cu2L1(H2O)2] (ClO4)2 (1) and [Cu2L2(ClO4)2] (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-flurophenol, respectively), have been synthesized and characterized. The electronic and magnetic properties of the complexes were studied by cyclic voltammetry and magnetic susceptibility. There are strong antiferromagnetic couplings between the two copper(II) centers in both complexes. The strongly electron-withdrawing fluorine groups in H2L2 weaken the antiferromagnetic exchange, but make the metal centers more easily reduced than its analog H2L1. The interactions of the complexes with calf thymus DNA were studied by UV?CVis and CD spectroscopic techniques. 相似文献
18.
With a modification of the cyclization procedure of Richman & Atkins [8] the two macrocycles 1,4,7-tritosyl-11-benzyl-1,4,7,11-tetraazacyclotetradecane ( 8 ) and 1,7,11-tritosyl-4-trityl-1,4,7,11-tetraazacyclotetradecane ( 15 ) were prepared. After selective cleavage of the benzyl and trityl group, respectively, one obtains the two key products 1,4,7-tritosyl-11-benzyl-1,4,7,11-tetraazacyclotetradecane ( 9 ) and 1,7,11-tritosyl-4-trityl-1,4,7,11-tetraazacyclotetradecane ( 16 ) which have three N-atoms protected by tosyl groups and one accessible for further reactions. To test some of the possibilities we have alkylated 9 and 16 with iodoacetamide, 1-tosyl-aziridine and acrylonitrile. After detosylation with HBr in glacial acetic acid in the presence of phenol mono-N-functionalized tetraazamacrocycles were thus obtained. The advantage of this synthesis is that the cyclization which is the most difficult step of the whole procedure, has to be done only once, regardless of the nature of the pendant arm. In addition a large number of derivatives can be prepared by varying the alkylation component. With Ni2+, Cu2+ and Zn2+ metal complexes of these new ligands were prepared and their IR. and VIS. spectra studied. In the case of the carbamoyl derivatives 12, 14 and 18 the Cu2+-complexes exist in two forms. Whereas at low pH the carboxamide group of the pendant arm is probably not bound to the metal ion, at high pH after deprotonation it coordinates in one of the axial positions. 相似文献
19.
《化学研究》2017,(3)
以钒酸铵为起始原料,在螯合配体存在下,利用水热合成法将其与二价第一行过渡金属阳离子在160℃反应得到了一个棕色块状化合物[Co(dien)_2]_2[V_6O_(17)]·3H_2O(1)(dien=二乙烯三胺),并用元素分析、红外光谱和X射线单晶衍射对之进行了定性分析.结果表明,化合物1属于单斜晶系,P2(1)/c空间群;其晶格参数为:a=1.613 4(4)nm,b=0.866 8(2)nm,c=1.398 1(4)nm;β=103.070(4)°;V=1.904 7(9)nm~3;ρ=2.016 g/cm~3;Z=2.化合物1是由钒氧层和[Co(dien)_2]~(2+)构成.这些钒氧层是由{VO}n螺旋链组成. 相似文献
20.