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1.
The electrochemical properties of n-sulfonatothiacalyx[4]arene (H4XNa4) complexes with [Co(dipy)3]3+ and Fe3+ ions were studied by means of cyclic voltammetry in aqueous solution at pH 2.5. The observed single-electron reduction of [Co(dipy)3]3+ bound extraspherically to the upper rim and Fe3+ ion bound intraspherically to the lower rim of n-sulfonatothiacalyx[4]arene in binary [Co(dipy)3]3+ · H3X5?, H3X5? · Fe3+, and ternary [Co(dipy)3]3+ · H3X5? · Fe3+ heterometal complexes was more difficult than in the free state. The reversible single-electron transfer to the metal ion results in lower binding energy ([Co(dipy)3]3+, ΔΔG 0 = 3.9 kJ/mol) or in full fast dissociation of the complex (Fe3+). The ternary complex in the solution forms the aggregates, in which inner encapsulated Fe(III) and Co(III) ions are not reduced on the electrode. Their quantitative reduction takes place by the relay mechanism of intra- and intermolecular electron transfer through electrochemically generated [Co(dipy)3]2+ outer ions.  相似文献   

2.
Centrosymmetric linear [Ar-H-Ar]+ and asymmetric linear [Ar---Ar-H]+ are two stable configurations of [Ar2H]+. Based on the global potential energy surface of [Ar2H]+ provided by our group recently, we calculated the vibrational spectra of [Ar---Ar-H]+ with total angular momentum J = 0 by time-dependent quantum mechanical method, and the influence of quantum tunneling effect on vibrational spectra was found. With the help of the observation on the eigenstate functions and the modified potential energy surface, assignments were made to the spectra. The strong coupling between the excited bending mode of [Ar-H-Ar]+ and the vibrational states of [Ar---Ar-H]+ was discussed.  相似文献   

3.
The reaction of [Cp*2RuBr]+Br with bromine in CH2Cl2 (CD2Cl2) in an inert atmosphere at room temperature produces the complexes [Cp*Ru(Br)C5Me4CH2Br]+Br3 (syn conformer), [Cp*Ru(Br)C5Me3(CH2Br)2]+ (syn and anti conformers), and [Ru(Br)(C5Me4CH2Br)2]+ (syn conformer). All complexes were characterized by 1H and 13C NMR spectroscopy; the former complex, by elemental analysis. These complexes were also prepared by the reaction of [Cp*RuC5Me4CH2]+BF4 with bromine in CH2Cl2. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2712–2718, December, 2005.  相似文献   

4.
The mono- and bisligands complexes formed by rare earth cation (Sc, Y) with pentazolato anion or cyclo-P5 anion, the all-nitrogen counterparts of metallocenes or the all-phosphorus counterparts of metallocenes, have been studied at hybrid basis sets level with the DFT method. The geometric parameters, binding energy and the charge distributions of these complexes were characterized. And their stable orders were obtained. Monoligand complexes incline to become bisligands complexes due to their destabilization. The charge transferring between ligand and metallic cation has affinity with the stability of complex. The possibility of forming stable [M(η 5-E5)2] (M = Sc, Y, E = N, P) complexes is predicted and they are viable synthetic targets theoretically, especially Sc(η 5-N5)2.  相似文献   

5.
The corrected selectivity coefficients of the ion exchange H+-Na+ and H+-NH4 + on ion-exchange resins based on C-tetramethylcalix[4]resorcinarene were calculated from the experimental data obtained from studying ion-exchange equilibria. The preference of the ion-exchange resins for cations increases in the sequence: Na+ < NH4 + < < H+, and the ion-exchange resin based on (2-furyl)hydroxymethyltetramethylcalix[4]resorcinarene has a higher preference for ammonium cations. According to the results of microcalorimetric measurements, the exchange H+-Na+ on this ion-exchange resin is accompanied by the highest change in the differential enthalpy. It follows from the quantum-chemical calculations that the introduction of a (2-furyl)hydroxymethyl group into the structure of the polymer induces additional electrostatic interactions between an ammonium cation and an elementary unit of the ion-exchange resin.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2560–2563, December, 2004.  相似文献   

6.
The ion-exchange equilibrium in network polymers obtained from cis-2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octahydroxycalix[4]arene by template synthesis on cations Na+, K+, and Ba2+ as matrices was studied. The selectivity coefficients of ion exchanges Ba2+-H+, Na+-H+, K+-H+, Na+-K+, and Na+-NH4 + were determined. The template synthesis enhanced the affinity of the polymers to matrix-forming cations by 6–8 kJ mol−1. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1919–1922, August, 2005.  相似文献   

7.
The effects of La3+ on inward K+ channels at plasma membrane in vicia guard cells are investigated using the whole-cell patch-clamp recording mode. It is shown that La3+ on both sides of plasma membrane blocks inward K+ currents in a concentration-dependent manner, indicating that La3+ binding sites may exist on both sides of plasma membrane in guard cells in vicia. The dose response is fitted by the Michaelis-Menten relation characterized by an inhibitor constant K i of 2.56±0.25 μmol · L−1 (outside membrane) and (1.18±0.11)×10−15 mol · L−1 (inside membrane). Intracellular La3+ has much stronger inhibitory effect on inward K+ currents than extracellular La3+ does, suggesting there may exist stronger binding sites inside membrane than outside membrane. Since ion channel activities of guard cells directly affect plant stomatal movement and water status, our results imply that rare earth elements might have potential practical values in regulating plant water status and strengthening plant drought endurance.  相似文献   

8.
The compound of composition [{Mo3O4(H2O)6Cl3}2(Na2Cl⊂ C30H30N 20O10)]Cl3⋅14H2O (1) was prepared by evaporation of a hydrochloric acid solution containing NaCl, the trinuclear aqua complex [Mo3O4(H2O)9]4+, and the macrocyclic cavitand cucurbit[5]uril (C30H30N20O10). X-ray diffraction analysis demonstrated that the cucurbit[5]uril molecule is closed on both sides by the cluster cations through hydrogen bonding between the CO groups of the cucurbit[5]uril portals and the aqua ligands of the oxo cluster. The inner cavity of the supramolecular adduct includes an unusual ionic associate Na+...Cl...Na+. The sodium cations are coordinated by five carbonyl oxygen atoms of each portal of the macrocycle. Compound 1 is the first structurally characterized complex, in which the macrocyclic cucurbit[5]uril ligand is directly coordinated to the alkali metal cation. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1513–1517, July, 2005.  相似文献   

9.
The imidazol side group of histidine has two nitrogen atoms capable of being protonated or participating in metal binding. Hence, histidine can take on various metal-bound and protonated forms in proteins. Because of its variable structural state, histidine often functions as a key amino acid residue in enzymatic reactions. Ab initio (HF and MP2) calculations were done in modeling the cation (H+, Li+, Na+, K+, Mg2+, Ca2+) interaction with side chain of histidine. The region selectivity of metal ion complexation is controlled by the affinity of the side of attack. In the imidazol unite of histidine the ring nitrogen has much higher metal ion (as well as proton) affinity. The complexation energies with the model systems decrease in the following order: Mg2+ > Ca2+ > Li+ > Na+ > K+. The variation of the bond lengths and the extent of charge transfer upon complexation correlate well with the computed interaction energies.  相似文献   

10.
The gas-phase conformations of transition metal cation-uracil complexes, [Ura+Cu]+ and [Ura+Ag]+, were examined via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra were measured over the IR fingerprint and hydrogen-stretching regions. Structures and linear IR spectra of the stable tautomeric conformations of these complexes were initially determined at the B3LYP/6-31G(d) level. The four most stable structures computed were also examined at the B3LYP/def2-TZVPPD level to improve the accuracy of the predicted IR spectra. Two very favorable modes of binding are found for [Ura+Cu]+ and [Ura+Ag]+ that involve O2N3 bidentate binding to the 2-keto-4-hydroxy minor tautomer and O4 monodentate binding to the canonical 2,4-diketo tautomer of Ura. Comparisons between the measured IRMPD and calculated IR spectra enable elucidation of the conformers present in the experiments. These comparisons indicate that both favorable binding modes are represented in the experimental tautomeric conformations of [Ura+Cu]+ and [Ura+Ag]+. B3LYP suggests that Cu+ exhibits a slight preference for O4 binding, whereas Ag+ exhibits a slight preference for O2N3 binding. In contrast, MP2 suggests that both Cu+ and Ag+ exhibit a more significant preference for O2N3 binding. The relative band intensities suggest that O4 binding conformers comprise a larger portion of the population for [Ura+Ag]+ than [Ura+Cu]+. The dissociation behavior and relative stabilities of the [Ura+M]+ complexes, M+ = Cu+, Ag+, H+, and Na+) are examined via energy-resolved collision-induced dissociation experiments. The IRMPD spectra, dissociation behaviors, and binding preferences of Cu+ and Ag+ are compared with previous and present results for those of H+ and Na+.
Graphical Abstract ?
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11.
The binding properties of two phenylketones (2a and 3a) and two ethylesters (2b and {3b) derived from p-tert-butyldihomooxacalix[4]arene or from p-tert-butylcalix[4]arene, in the cone conformation, towards transition (Ag+, Ni2+, Cu2+, Co2+, Zn2+, Fe2+ and Mn2+) and heavy (Cd2+, Hg2+ and Pb2+) metal cations have been determined by extraction studies with metal picrates and liquid membrane transport experiments with the same salts. The affinity of these ligands for Ag+ has also been investigated by 1H NMR spectroscopy. Both ketones are better extractants than the esters, and show a strong preference for Ag+, while Cu2+ is the most extracted cation with the esters. 1H NMR titrations with AgSO3CF3 indicate 1 : 1 complexes for all ligands, those with ketones are more stable, on the NMR time scale, than those with esters. Both esters are good carriers for Ag+, and 2b exhibits the highest transport rate (4.7 mol h-1) found until now with dihomooxacalix[4]arene derivatives.  相似文献   

12.
Our recent studies on the synthesis of metallacarboranes based on the cationic species [(Carb)M]+ are summarized. The labile complexes [Carb’M(Solv)3]2+ (Carb’ = 9-SMe2- 7,8-C2B9H10; M = Rh or Ir) and [Carb’ Fe(C6H6)]+ were suggested to use as synthons. The new method was employed to synthesize a great variety of sandwich, half-sandwich, and tripledecker complexes.  相似文献   

13.
Four new azocalix[4]arenes {5,11,17,23-tetrakis[(2-hydroxy-5-tert-butylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (1), 5,11,17,23-tetrakis[(2-hydroxy-5-nitro phenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (2), 5,11,17,23-tetrakis[(2-amino-5-carboxylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (3) and 5,11,17,23-tetrakis[(1-amino-2-hydroxy-4-sulfonicacidnapthylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (4)} have been synthesized from p-tert-butylphenol, p-nitrophenol, p-aminobenzoic acid and 1-amino-2-hydroxy-4-sulphonic acid by diazo coupling reaction with p-aminocalix[4]arene. The resulting ligands (14) were treated with three transition metal salts (e.g., CuCl2·2H2O, NiCl2·6H2O or CoCl2·6H2O). Cu(II), Ni(II) and Co(II) complexes of the azocalix[4]arene derivatives were obtained and characterized by UV-vis, IR, 1H-NMR spectroscopic techniques and elemental analysis. All the complexes have a metal:ligand ratio of 2:1. The Cu(II) and Ni(II) complexes of azocalix[4]arenes are square-planar, while the Co(II) complexes of azocalix[4]arenes are octahedral with water molecules as axial ligands. The solvent extraction of various transition metal cations from the aqueous phase to the organic phase was carried out by using azocalix[4]arenes (14). It was found that, azocalix[4]arenes 1, 2 and 3 examined selectivity for transition metal cations such as Ag+, Hg+ and Hg2+. In addition, the thermal stability of metal:azocalix[4]arene complexes were also reported. Dedicated to Prof. Dr. Mustafa Yılmaz on the occasion of his 50th birthday  相似文献   

14.
1H NMR titration and X-ray diffraction analysis revealed that [Ru(bipy)3]2+ forms an outer-sphere inclusion complex with p-sulfonatothiacalix[4]arene in a ratio of 1: 1 in both aqueous solutions and the solid state. According to cyclic voltammograms and fluorimetric data, the outer-sphere association of [Ru(bipy)3]2+ with p-sulfonatothiacalix[4]arene changes the reversible character of the electrochemical oxidation of [Ru(bipy)3]2+ and lowers its emission intensity. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1863–1870, September, 2008.  相似文献   

15.
The dibenzo[3n]crown-n were synthesised starting from bis[2-(o-hydroxyphenoxy)ethyl]ether obtained from bis[2-(o-formylphenoxy)ethyl]ether via Baeyer-Villiger oxidation in H2O2/CH3COOH in a good yield. The cyclic condensation ofbis[2-(o-hydroxyphenoxy)ethyl]etherwith tri- and tetraethylene glycol bisdichlorides andthe bisditosylate of pentaethylene glycol in DMF/Me2CO3 afforded the large cyclic ethers of dibenzo[21]crown-7, dibenzo[24]crown-8 and dibenzo[27]crown-9. The structures were analysed with IR, 1H NMR, 13C NMR and low-resolution mass spectroscopy methods. The Na+, K+, Rb+ and Cs+ cations' recognition of the molecules were conducted withsteady-state fluorescence spectroscopy. The 1:1 association constants, Ka, in acetonitrile were estimated. Dibenzo[21]crown-7 was the best both for K+ and Rb+ binding but showed too small an effect on Cs+. Dibenzo[24]crown-8 exhibited the binding power in the order of Rb+ > K+ > Na+ > Cs+. However, dibenzo[27]crown-9 displayed marked binding with only K+ but not with Rb+ or with Cs+ cations probably due to the heavy atom effect of fluorescence quenching.  相似文献   

16.
The complexation reactions between La3+, Y3+ and Ce3+ cations with the macrocyclic ligand, kryptofix 21, were studied in methanol-acetonitrile (MeOH-AN) and methanol-methylacetate (MeOHMeOAc) binary mixed solvent solutions at different temperatures using the conductometric method. The conductance data show that in most solvent systems, the kryptofix 21 forms a 1: 1 [M: L] complex with La3+, Y3+ and Ce3+ metal cations, but in the case of Y3+ cation in pure methylacetate, in addition of formation of a 1: 1 [ML] complex, 1: 2 [ML2] and 1: 3 [ML3] complexes are formed in solution. In the case of Ce3+cation, a 1: 1 [ML] and also a 1: 2 [ML2] complexes are formed in this solvent system at all studied temperatures. The electrical conductance data in acetonitrile, show that a 1: 1 [ML] and also a 1: 2 [ML2] complexes are formed between the ligand and La3+ and Ce3+ metal cations at different temperatures. The stability constants of the 1: 1 [ML] complexes were determined using the conductometric data and a computer program, GENPLOT. A non-monotonic relationship was observed between logK f of the 1: 1 complexes with the composition of the binary solvent solutions which was discussed in term of solvent-solvent interactions and also preferential solvation of the metal cations and the ligand in solutions. The selectivity order of the ligand for the metal cations in MeOH–AN and MeOH–MeOAc binary solvent solutions, at 25°C was found to be: Y3+ > La3+ > Ce3+ and La3+ > Y3+ > Ce3+, respectively. The values of the standard thermodynamic quantities (ΔH c ° and ΔS c ° ) for formation of the 1: 1 complexes were obtained from temperature dependence of the stability constans of the complexes and the results show that the thermodynamics of the complexation reactions between kryptofix 21 and La3+, Y3+ and Ce3+ cations, is affected by the nature and composition of the mixed solvents systems.  相似文献   

17.
An analysis of the structures of minerals with [Hg2]2+ dumbbells including poyarkovite [Hg2]3Cl2O2, shakhovite [Hg2]2Sb(OH)3O3, vasilyevite Hg20O6I3Br2Cl(CO3), and kelyanite [Hg2]6[SbO6]BrCl2 was carried out. The determining factor in structure formation is the ordering of the centers of the cluster groups of mercury and large anions by systems of equidistant parallel planes with d hkl ~ 2.5–4.5 Å. The different combinations of atoms and fragments in the structure are ordered by their own pseudotranslation lattices; this probably reflects the stages of crystallization. The crystal structures under study are examples of balance between the local interatomic interactions and the forces that create long-range order for different stoichiometries, masses, and sizes of components.  相似文献   

18.
《Analytical letters》2012,45(5):768-775
Nine series of chromogenic mono- (A1-A2) and di- (B1-B7) substituted azocalix[4] arene analogues containing more than one azo group were described. Different chelating agents like ester and ketone moieties were grafted on the lower rim position of azocalix[4]arenes. The selective extraction properties of Fe3+ cation were studied by liquid-liquid extraction. This extraction process was carried out by using compounds A1-A2 and B1-B7. The results proved that coupling of phenylazo groups onto the upper rim of azocalix[4]arenes yielded greater efficiency and selectivity for carrying the Fe3+ cation in the extraction process at pH 2.2.  相似文献   

19.
Synthesis of water-soluble potassium salts of carboxymethyl derivatives of calix[4]pyrogallols and dodeca(carboxylatomethyl)tetramethylcalix[4]pyrogallol (L) complexes with transition metal ions (Cu2+, Fe3+, La3+) is described. Their structures in the solid state and in solution were characterized by NMR spectroscopy, ESR, and IR spectroscopy. Calix[4]pyrogallol dodecacarboxylates exist in the rccc-configuration. Calix[4]pyrogallol with methyl substituents at the lower rim in a wide range concentrations exists in water predominantly in the dimeric form. The obtained polynuclear transition metal complexes possess less symmetric structure than potassium salt of calix[4]pyrogallol (K12L). All studied complexes contain water molecules bound by rather strong hydrogen bonds. At room temperature the Fe4L complex is characterized by the environment of the Fe3+ ions close to octahedral. The absence of signals in the ESR spectrum of the Cu6L complex indicates the strong antiferromagnetic interaction Cu2+-Cu2+.  相似文献   

20.
The equilibrium constants and thermodynamic parameters for complex formation of 18-Crown-6 (18C6) with Tl+, Pb2+, Hg2+, and Zn2+ metal cations have been determined by conductivity measurements in methanol (MeOH)-water (H2O) binary solutions. 18-Crown-6 forms 1:1 complexes with Hg2+ and Zn2+ cations, but in the case of Tl+ and Pb2+ cations, in addition to 1:1 stoichiometry, 1:2 (ML2) complexes are formed in some binary solvents. The thermodynamic parameters (ΔH c0 and ΔS c0), which were obtained from the temperature dependences of equilibrium constants, show that in most cases the complexes are enthalpy destabilized but entropy stabilized. Non-linear behavior is observed between the equilibrium constants (log K f ) of complexes and the composition of the mixed solvent. The selectivity of the ligand for these metal cations is sensitive to the solvent composition, and, in some cases, the selectivity order is reversed in certain compositions of the mixed solvent. The results also show that the mechanism of complexation reactions and the stoichiometry of complexes of some metal cations change with the nature and even with the composition of the mixed solvent. The article was submitted by the authors in English.  相似文献   

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