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1.
Syntheses of copper(II) complexes of 20-membered and 15-membered aza macrocycles 1,3,6,8,11,13,16,18-octaaza-2,7,12,17-tetrachlorocycloeicosane (OTCE, [20]-N8) and 1,3,6,8, 11,13-hexaazacyclopentadecane (HCPD, [15]-N6) involving metal template condensation between 1,2-diaminoethane, trichloromethane and dichloromethane, respectively, are reported. Formulation of [Cu4(OTCE)(H2O)8]Cl8 and [Cu3(HCPD)(H2O)6]Cl6 · 2H2O and the ligand hydrochlorides OTCE · 8HCl and HCPD · 6HCl are supported by elemental analyses, conductivity measurements, and spectral studies. For a comparative cavity size effect on the stability constant, potentiometric measurements on the copper complexes of the generated macrocycles [15]-N6 and [20]-N8 and the structurally related larger macrocycle 1,3,6,8,11,13,16,18,21,23-decaaza-2,2,7,7,12,12,17,17,22,22-decachlorocyclopentacosane (DDCP, [25]-N10, prepared recently) have been performed in aqueous solution at 25°C (μ = 0.1 M KNO3). Very high stability constants obtained for reaction Cu2+ + A ? CuA2+ (A = ligand, log K = 20.51 and 25.87, respectively, for OTCE and DDCP systems) are a reflection on the folding of the ligand to provide a small cavity suitable for fitting of the copper ion. Further, a high equilibrium constant value for CuA2+ + Cu2+ ? Cu2A4+ (OTCE system, log K = 14.59) or Cu2A4+ + Cu2+ ? Cu3A6+ (DDCP system, log K = 16.69) is due to suitable fitting of two and three copper ions in the 20-membered and 25-membered ring cavity of OTCE and DDCP, respectively.  相似文献   

2.
The present work describes the preparation and characterization of some metal ion complexes derived from 4-formylpyridine-4 N-(2-pyridyl)thiosemicarbazone (HFPTS). The complexes have the formula; [Cd(HFPTS)2H2O]Cl2, [CoCl2(HPTS)]·H2O, [Cu2Cl4(HPTS)]·H2O, [Fe (HPTS)2Cl2]Cl·3H2O, [Hg(HPTS)Cl2]·4H2O, [Mn(HPTS)Cl2]·5H2O, [Ni(HPTS)Cl2]·2H2O, [UO2(FPTS)2(H2O)]·3H2O. The complexes were characterized by elemental analysis, spectral (IR, 1H-NMR and UV–Vis), thermal and magnetic moment measurements. The neutral bidentate coordination mode is major for the most investigated complexes. A mononegative bidentate for UO2(II), and neutral tridentate for Cu(II). The tetrahedral arrangement is proposed for most investigated complexes. The biological investigation displays the toxic activity of Hg(II) and UO2(II) complexes, whereas the ligand displays the lowest inhibition activity toward the most investigated microorganisms.  相似文献   

3.
A dimeric dichloro-bridged copper(II) complex [Cu2(pdon)2Cl4] · 2DMF (1) and two mononuclear copper(II) complexes [Cu(pdon)(DMSO)Cl2] · DMSO · H2O (2) and [Cu(pdon)3] · (ClO4)2 · 2.25CH3CN · 6H2O (3) (pdon = 1,10-phenanthroline-5,6-dione) have been synthesized and characterized. Variable-temperature magnetic susceptibility studies indicate the existence of weak anti-ferromagnetic coupling in the binuclear complex. The interaction of these complexes with CT-DNA (calf thymus DNA) has been studied using absorption and emission spectral methods. The apparent binding constants (K app) for 1, 2 and 3 are 5.20 × 105, 2.68 × 105 and 7.05 × 105 M?1, respectively, showing moderate intercalative binding modes. All of these complexes cleave plasmid DNA to nicked DNA in a sequential manner as the concentration or reaction time is increased. The cleavage mechanism between the complex and plasmid DNA is likely to involve singlet oxygen 1O2 and ?OH as reactive oxygen species.  相似文献   

4.
Two complexes, [Cu2(TFSA)(2,2′-bpy)4]?·?TFSA?·?8H2O (1) and {[Cu(4,4′-bpy)(H2O)2]?·?TFSA?·?6H2O} n (2) (H2TFSA?=?tetrafluorosuccinic acid, 2,2′-bpy?=?2,2′-bipyridine, and 4,4′-bpy?=?4,4′-bipyridine), have been synthesized and structurally characterized by X-ray structural analyses. Complex 1 is a binuclear molecule bridged by TFSA ligands; 2 is a 1-D chain bridged by 4,4′-bpy ligands. The asymmetric units of the two complexes are composed of cationic complexes [Cu2(TFSA)(2,2′-bpy)4]2+ (1) and [Cu(4,4′-bpy)(H2O)2]2+ (2), free TFSA anion, and independent crystallization water molecules. A unique 2-D hybrid water–TFSA anionic layer by linkage of {[(H2O)8(TFSA)]2?} n fragments consisting of 1-D T6(0)A2 water tape and TFSA anionic units by hydrogen bonds in 1 was observed. Unique 2-D hybrid water–TFSA anionic layer generated by the linkage of {[(H2O)6(TFSA)]2?} n fragments consisting of cyclic water tetramers with appended water molecules and TFSA anionic units, and 1-D metal–water tape [Cu–H2O?···?(H2O)6?···?H2O?] n in 2 were found. 3-D supramolecular networks of the two complexes consist of cationic complexes and water–TFSA anionic assemblies connected by hydrogen bonds.  相似文献   

5.
Crystals of the formula (An)3[Cu4Cl7] (I) and (An)3[Cu8Cl10(C? CCH2OH)]· 2H2O (II) were obtained in the system AnCl-CuCl-H2O-HC? CCH2OH [An is the anilinium cation (C6H5NH 3 + )] and studied by X-ray diffraction analysis (DARCH diffractometer, λMoKα, θ/2θ scan mode; 1121 and 2433 unique reflections with F≥4Σ(F), R = 0.064 and 0.044 for I and II, respectively). Ciystals I are orthorhombic, space group Pbnm, Z = 4. a = 21.65(1), b = 11.006(5). c = 11.068(6) Å; ciystals II are triclinic, space group P-l, Z = 2, a = 14.94(1), b = 12.242(8). c = 11.341(7) Å, α = 106.77(5), β = 92.05(6), γ = 113.38(5)°. In contrast to I, the anionic copper acetylenide π-complex contains the propargylium ion whose terminal C? C group acts as a double bridging π, Σ-ligand sim ultaneously bonded to four copper(I) atoms. Structural genesis of [Cu4Cl7]3? n] (I) and [Cu8C110(C = CCH2OH)]3? n (II) anions is considered.  相似文献   

6.
Reactions of the rigid–flexible N-heterocycle 1,3-bis(5-(pyridine-2-yl)-1,2,4-triazole-3-yl) propane (H2L) with MCl2 (M = Fe, Co, Cu or Zn) gave coordination complexes, {[Fe 2 III Cl4(H2L)2]·2Cl}·EtOH·H2O (1), {[Co3Cl5(HL)]·H2O} n (2), {[Co4Cl4(H2L)2(H2O)4]·[CoCl4]2}·H2O (3), [Cu2Cl3(HL)(H2O)]6·5H2O (4), [Cu 2 II CuICl4(HL)] n (5), {[Zn2Cl2(L)H2O]·H2O} n (6) and [Zn4Cl6(HL)2] (7), which have been characterized by single-crystal X-ray diffraction. Structural analysis reveals that the pyridine triazole ligand attains versatile coordination modes in these complexes. Complexes 1, 3, 4 and 7 consist of 0D clusters with binuclear or tetranuclear units; complex 2 presents a 2D network accompanied by HL? and chloride bridges; complexes 5 and 6 show 1D chains with [Cu3] and [Zn2] subunits. In addition, the electrospray ionization mass spectrometry properties of selected complexes were investigated, revealing the stabilities and structural states of these complexes in solution. These results indicate that H2L is an excellent multiconnection linker for the construction of diverse coordination complexes.  相似文献   

7.
Eight new copper(II) complexes with halo-aspirinate anions have been synthesized: [Cu2(Fasp)4(MeCN)2]?·?2MeCN (1), [Cu2(Clasp)4(MeCN)2]?·?2MeCN (2), [Cu2(Brasp)4(MeCN)2]?·?2MeCN (3), {[Cu2(Fasp)4(Pyrz)]?·?2MeCN} n (4), {[Cu2(Clasp)4(Pyrz)]?·?2MeCN} n (5), [Cu2(Brasp)4(Pyrz)] n (6), [Cu2(Clasp)4(4,4′-Bipy)] n (7), and [Cu2(Brasp)4(4,4′-Bipy)] n (8) (Fasp: fluor-aspirinate; Clasp: chloro-aspirinate; Brasp: bromo-aspirinate; MeCN: acetonitrile; Pyrz: pyrazine; 4,4′-Bipy: 4,4′-bipyridine). The crystal structure of two 2 and 4 have been determined by X-ray diffraction methods. All compounds have been studied employing elemental analysis, IR, and UV-Visible spectroscopic techniques. The results have been compared with previous data reported for complexes with similar structures.  相似文献   

8.
EPR-Investigations of α-Dichloro-bis[chloro?bis(N,N?diethyldiselenocarbamato)molybdänum(V)] dichloride, [Mo2Cl4(däsc)4]Cl2. Preparation and bonding properties of the coordination sphere of [Mo2Cl4(däsc)4]Cl2 studied by EPR, are reported. The EPR-spectrum at 77°K can be described by an axial symmetric spin-HAMILTONian, the parameters of which are g| = 2.046, g|= 1.996, A| = 53.5 · 10?4 cm?1, and A| = 22.8 · 10?4 cm?1. No 77Se-ligand hyperfine structure could be observed. The very high g-values are explained as being caused by strong ligand spin-orbit interaction, CT-contributions and a high degree of co valency of tho Mo? Se bond. Using an MO-model of the symmetry C4v, the bonding parameters of the first coordination sphere have been calculated.  相似文献   

9.
Crystallochemical treatment of the Nieuwland reaction is carried out on the basis of structural data obtained for crystalline acetylene complexes of the formulas NH4Cu8Cl9·4C2H2·1/2HCu2Cl3·H2O (I), NH4Cu3Cl4·C2H2 (II), KCu8Cl9·4C2H2·1/2HCu2Cl3·H2O (III), KCu3Cl4·C2H2 (IV), (NH4)2Cu3Cl5·4/9H2O·(xC2H2) with x=0 (Va), 1/9 (Vb), and 4/9 (Vc) and divinylacetylene (DVA) copper chloride compounds 2CuCl·DVA (VI) and 3CuCl·DVA (VII). Because of the π-coordination of a copper atom, the C≡C bond of the acetylene molecule is activated, as indicated by its significant (up to 1.32 Å) stretch (complexes I and II). The zeolite-like structure of complexes Va-Vc, which form in a catalytic solution, is realized as an infinite {[Cu108Cl168(H2O)16]60?}n anion with discrete [Cl(NH4)6]5+ cations inside. In this structure, only 16 Cu(1) atoms have a trigonal-pyramidal environment with the oxygen atom of the crystallization water located in the vertex (dCu?O=2.79 Å). Under the liquid-phase conditions of the Nieuwland reaction, these copper atoms are active centers stimulating the reaction to the subsequent acetylene oligomerization due to the π-interaction with the C2H2 molecule. The mutual arrangement of the catalytically active Cu(1) atoms in structure Va serves as a matrix for the synthesis of DVA, as shown by the structure of the 2CuCl·DVA adduct.  相似文献   

10.
Reactions of copper salts, zoledronic acid, and 2,2′-bipyridine/1,10-phenanthroline in aqueous ethanolic solutions afforded four phosphonate oxygen-bridged copper complexes, Cu(bipy)(H4zdn)(HSO4) (1), [Cu2(bipy)2(H2zdn)(H2O)(Cl)]·4H2O (2), [Cu2(phen)2(H2zdn)(H2O)(Cl)]·2.5H2O (3), and [Cu3(bipy)3(H4zdn)(H2zdn)(SO4)]·5H2O (4) (H5zdn = zoledronic acid, bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline). The copper centers of 14 have square pyramidal coordination geometries. The Cu(II) ions are coordinated to bipy/phen, zoledronate, and HSO4?/Cl? forming mononuclear units for 1, dinuclear for 2 and 3, and trinuclear for 4. These building units are further extended into 3-D supramolecular networks via multiple hydrogen bond interactions. Temperature-dependent magnetic properties of 2 and 4 suggest weak antiferromagnetic coupling (J = ?4.53(8) cm?1 for 2, J = ?1.69(4) cm?1 for 4). The antitumor activity of 2 was evaluated against the human lung cancer cell line and indicates effective time- and dose-dependent cytotoxic effects.  相似文献   

11.
The Crystal Structures of [Cu2Cl2(AA · H+)2](NO3)2 and [AA · H+]Picr? (AA · H+ = Allylammonium; Picr? = Picrat) By an alternating current electro synthesis the crystal-line π-complex [Cu2Cl2(AA · H+)2](NO3)2 has been obtained from CuCl2 · 2H2O, allylamine (AA), and HNO3 in ethanolic solution. X-ray structure analysis revealed that the compound crystallized in the monoclinic system, space group P21/a, a = 7.229(3), b = 7.824(3), c = 26.098(6) Å, γ = 94.46(5)°, Z = 4, R = 0.025 for 2 023 reflections. The crystal structure is built up of CunCln chains which are connected by π-bonding bidentate AA · H+ …? ON(O)O …? H+ · AA units. For comparision with the above complex the structure of [AA · H+]Picr? (Picr? = picrate anion) is also reported.  相似文献   

12.
13.
Three dinuclear copper(II) complexes with the anti-inflammatory drug Fenoprofen [Hfen, 2-(3-phenoxyphenyl)propionic acid] and nitrogen donors of general formula [Cu2(fen)4(L)] n were prepared from [Cu2(fen)4(dmf)2]·2H2O (1) [dmf?=?N,N′-dimethylformamide; L?=?4,4′-bipyridine (2), pyrazine (3), and 2,5-dimethylpyrazine (4)]. The new complexes were characterized by chemical analysis, spectroscopic, and thermogravimetric techniques. Antioxidant properties of 1–4 were evaluated for superoxide-dismutase-mimic activity employing the XTT method. Complex 2 presented the highest antioxidant activity (IC50?=?0.260?µmol?L?1). Anti-inflammatory properties of 2 were evaluated employing carrageenan-induced paw edema in mice, revealing that the Fenoprofen–copper(II) complex containing 4,4′-bipyridine does not present enhanced anti-inflammatory activity compared to the uncomplexed parent drug Fenoprofen calcium salt.  相似文献   

14.
Self-assembly of a flexible tripodal ligand, 1,3,5-tris(1,2,4-triazol-1-ylmethyl)benzene (ttmb) and organometallic carboxylate 1,1'-bis(3-carboxy-1-oxopropyl)-ferrocene (H2bfcs) with Cd(Ac)2?·?2H2O or CdCl2?·?2.5H2O yi elds two 2-D binodal (3,4)-connected complexes {[Cd2(bfcs)(Hbfcs)2(ttmb)2]?·?10H2O} n (1) and [CdCl(Hbfcs)(ttmb)] n (2), exhibiting the same topological type (42?·?6)(42?·?63?·?8). Both exhibit a layer structure, which is generated through 1-D undulated ladders connected by organometallic carboxylate, bfcs2? (in 1), or Cl? (in 2). Differential pulse voltammetry experiments indicate that half-wave potentials are slightly higher than that of H2bfcs. Both complexes exhibit similar weak fluorescent emissions at room temperature.  相似文献   

15.
Density functional theory calculations, with an effective core potential for the copper ion, and large polarized basis set functions have been used to construct the potential energy surface of the Cu+·(CO)n (n = 1–3) complexes. A linear configuration is obtained for the global minimum of the Cu+·CO and Cu+·(CO)2 complexes with a bond dissociation energy (BDE) of 35.9 and 40.0 kcal mol-1, respectively. For the Cu+·(CO)3 complex, a trigonal planar geometry is obtained for the global minimum with a BDE of 16.5 kcal mol?1. C-coordinated copper ion complexes exhibit stronger binding energy than O-coordinated complexes as a result of Clp → 4s σ-donation. The computed sequential BDEs of Cu+·(CO)n (n = 1–4) complexes agree well with experimental findings, in which the electrostatic energy and σ-donation play an important role in the observed trend.  相似文献   

16.
Four CuII and CoII complexes–[Cu(L1)Cl2(H2O)]3/2H2O · 1/2EtOH, [Cu(L1)2Cl2]6H2O, [Co(L1)Cl2]3H2O · EtOH, and [Co2(L1)(H2O)Cl4]1.5H2O · EtOH (L1 = 2,4,6-tri(2-pyridyl)-1,3,5-triazine; TPT)–were synthesized by conventional chemical method and used to synthesize another four metal complexes–[Cu(L1)I2(H2O)]6H2O, [Cu(L1)2I2]6H2O, [Co(L1)I(H2O)2]I · 2H2O, and [Co2(L1)I4(H2O)3]–using tribochemical reaction, by grinding it with KI. Substitution of chloride by iodide occurred, but no reduction for CuII or oxidation of CoII. Oxidation of CoII to CoIII complexes was only observed on the dissolution of CoII complexes in d6-DMSO in air while warming. The isolated solid complexes (CuII and CoII) have been characterized by elemental analyses, conductivities, spectral (IR, UV-Vis, 1H-NMR), thermal measurements (TGA), and magnetic measurements. The values of molar conductivities suggest non-electrolytes in DMF. The metal complexes are paramagnetic. IR spectra indicate that TPT is tridentate coordinating via the two pyridyl nitrogens and one triazine nitrogen forming two five-membered rings around the metal in M : L complexes and bidentate via one triazine nitrogen and one pyridyl nitrogen in ML2 complexes. In binuclear complexes, L is tridentate toward one CoII and bidentate toward the second CoII in [Co2(L1)Cl4]2.5H2O · EtOH and [Co2(L1)I4(H2O)3]. Electronic spectra and magnetic measurements suggest a distorted-octahedral around CuII and high-spin octahedral and square-pyramidal geometry around CoII.  相似文献   

17.
Low-energy reactive collisions between the negative molecular ion of a tetrachlorodibenzo-p-dioxin (TCDD) and oxygen inside the collision cell of a triple-stage quadrupole mass spectrometer produce a substitution ion [M ? Cl + O]?, a phenoxide ion [C6H4-nO2Cln], [M ? HCl], and Cl? by which 1,2,3,4-, 1,2,3,6/1,2,3,7- and 2,3,7,8-TCDD isomers can be distinguished either directly or on the basis of intensity ratios. The collision conditions have an important effect on the relative abundances. Energy- and pressure-resolved curves show that the ions formed by a collisionally activated reaction (CAR) process, i.e. [M ? Cl + O]? and [C6H4-n,O2Cln], are favoured by a high pressure of oxygen (3-6 mTorr) (1 Torr = 133.3 Pa) and a low collision energy (0.1-7 eV), whereas the ions formed by a collisionally activated dissociation (CAD) process, i.e. [M ? HCl] and Cl?, are favoured by high pressure and high energy. By choosing a relatively low collision energy (5 eV) and high pressure (4 mTorr), the CAR and CAD ions can be clearly detected.  相似文献   

18.
[In(dm4bt)Cl3(MeOH)]?·?0.5dm4bt (1) (dm4bt is 2,2′‐dimethyl‐4,4′‐bithiazole) and [In(4bt)Cl3(MeOH)] (2) (4bt is 4,4′‐bithiazole) were prepared from the reaction of 4,4′‐bithiazole and 2,2′‐dimethyl‐4,4′‐bithiazole with InCl3?·?4H2O in methanol, respectively. [In(4bt)Cl3(DMSO)] (3) was also prepared from recrystallization of 2 in DMSO. These complexes were characterized by IR, UV‐Vis, 1H NMR, 13C{1H} NMR, and luminescence spectroscopy and their structures were studied by single‐crystal X‐ray crystallography. The thermal stabilities of 1 and 3 were studied by thermogravimetric and differential thermal analyses.  相似文献   

19.
Two ruthenium(II) complexes [Ru(MeIm)4(L)]2+ (L?=?2-(imidazo-4-group)-1H-imidazo-[4,5-f][1,10]phenanthroline, 2-(thiophene-2-group)-1H-imidazo[4,5-f][1,10]phenanthroline, MeIm?=?1-methylimidazole) have been synthesized according to literature and structurally characterized. The interaction of the complexes with calf thymus DNA has been explored using electronic absorption titration, competitive binding experiment, circular dichroism, thermal denaturation, and viscosity measurements. The results show that both complexes could bind DNA in a intercalation mode and the DNA-binding affinity of [Ru(MeIm)4(tip)]2+ (K b?=?(7.2?±?0.3)?×?105?(mol?L?1)?1) is greater than that of [Ru(MeIm)4(iip)]2+ (K b?=?(6.1?±?0.2)?×?105?(mol?L?1)?1).  相似文献   

20.
Cage-opened diamondoid tetracyclo[7.3.1.14,12.02,7]tetradeca-6,11-diene forms complexes with AgNO3 and CuCl. The latter crystallized from acetonitrile in polymeric form [Cu2Cl2(CH3CN)(diene)]n; in the presence of 2,2′-bipyridine, a double-charged monomeric Cu(I)-complex [Cu2(bipy)2(diene)]2+ formed. Both complexes were structurally characterized through X-ray crystal diffraction analysis.  相似文献   

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