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1.
A new family of 2p‐3d‐4f hetero‐tri‐spin complexes [Ln(hfac)3{Cu(hfac)2(NIT‐3 PyPh)}2] (Ln=Gd ( 1 ), Tb ( 2 ), Dy ( 3 ), Ho ( 4 ); NIT‐3 PyPh=2‐[4‐(3‐pyridinylmethoxy)phenyl]‐4,4,5,5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide; hfac=hexafluoroacetylacetonate) have been synthesized. Four complexes possess a 1D chain structure in which two radical ligands join two Cu(hfac)2 molecules to form a [{Cu(hfac)2‐rad)}2] dimer cycle and the dimer rings are linked by Ln(hfac)3 units. Magnetic studies show that ferromagnetic exchange couplings exist between the coordinated NO groups of radical ligands and metal ions. Field‐induced slow relaxation of the magnetization was observed in the Tb and Dy compounds.  相似文献   

2.
Four lanthanide-nitronyl nitroxide radical complexes, [Ln(hfac)3(NIT-3Methien)2] (Ln = Pr (1), Tb (2), Dy (3), Ho (4); hfac = hexafluoroacetylacetonate; NIT-3Methien = 2-(3-methylthiophene)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), have been synthesized, and structurally and magnetically characterized. Single-crystal X-ray diffraction shows that 1–4 have similar mononuclear tri-spin structures in which central Ln(III) ions are eight coordinate by two NIT-3Methien radicals and three hfac coligands. The magnetic studies indicate that there are antiferromagnetic interactions between Ln(III) ions and radicals in 1, 2, and 4, while ferromagnetic interactions are present in 3. The luminescence properties of 2 and 3 were studied.  相似文献   

3.
This paper assesses the adsorption characteristics of Titan yellow and Congo red on CoFe2O4 magnetic nanoparticles. The adsorption behavior of Titan yellow and Congo red from aqueous solution onto CoFe2O4 magnetic nanoparticles has been determined by investigating the effects of pH, concentration of the dye, amount of adsorbent, contact time, ionic strength and temperature. Experimental results indicated that CoFe2O4 nanoparticles can remove more than 98 % of each dye under optimum operational conditions of a dosage of 15.0 mg CoFe2O4, pH 3.0, initial dye concentration of 22–140 mg L?1, and contact times of 2.0 and 15.0 min for Congo red and Titan yellow, respectively. Langmuir and Freundlich isotherm models have been used to evaluate the ongoing adsorption kinetic equations. Regeneration of the saturated adsorbent was possible by NaCl/acetone solution as eluent. The maximum adsorption capacities were 200.0 and 212.8 mg dye per gram adsorbent for Congo red and Titan yellow, respectively. With the help of adsorption isotherm, thermodynamic parameters such as free energy, enthalpy and entropy have been calculated. On the basis of pseudo-first-order and pseudo-second-order kinetic equations, different kinetic parameters have been obtained.  相似文献   

4.
Four radical–Ln(III)–radical complexes, [Ln(hfac)3(NITPhSCH3)2] (Ln?=?Gd (1), Dy (2), Er (3), Ho (4); hfac?=?hexafluoroacetylacetonate; NITPhSCH3?=?4′-thiomethylphenyl-4,4,5,5tetramethyl-imidazoline-1-oxyl-3-oxide), have been synthesized, and structurally and magnetically characterized. The X-ray crystal structures show that the structures of the four complexes are similar, consisting of isolated molecules in which Ln(III) ions are coordinated by six oxygen atoms from three hfac and two oxygen atoms from nitronyl radicals. The temperature dependencies of magnetic susceptibilities for the four complexes show that in the Gd(III) complex, ferromagnetic interactions between Gd(III)–radical and antiferromagnetic interactions between the radicals coexist with J Rad–Gd?=?1.09?cm?1, J Rad–Rad?=??1.85?cm?1.  相似文献   

5.
The complex formation between Zn2+, Cd2+ and Pb2+ ions with macrocyclic ligand, tetrathia12-crown-4 (12S4) was studied in dimethylsulfoxide (DMSO)–nitrobenzene binary mixtures at different temperatures using conductometric and 1H NMR methods. In all cases, 12S4 found to form 1:1 complexes with these cations. The formation constants of the resulting 1:1 complexes in different solvent mixtures were determined by computer fitting of the resulting molar conductance- and chemical shift-mole ratio data. There is an inverse relationship between the complex stability and the amount of DMSO in the solvent mixtures. The stability of the resulting M2+-12S4 complexes found to decrease in the order Pb2+ > Cd2+ > Zn2+. The values of ?H°, ?S° and ?G° for complexation reactions were evaluated from the temperature dependence of formation constants via van’t Hoff method. The obtained results revealed that, in all cases, the complexes are enthalpy stabilized, but entropy destabilized and the values of ?H° and ?S° are strongly depend on the nature of medium. There is also a linear relationship between all ΔH° and TΔS° values indicating the existence of entropy–enthalpy compensation in complexation of the three cations and ligand in the solvent systems studied.  相似文献   

6.
A series of new lanthanide-radical complexes [{Ln(hfac)3}2(NITPhIM)2] (Ln = Nd (1), Eu (2), Tb (3), Er (4); hfac = hexafluoroacetylacetonate; NITPhIM = 2-[4-(1-imidazole)phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) have been prepared and characterized. Single crystal X-ray diffraction analyses reveal that these complexes are isostructural with one-dimensional chain structures. These consist in Ln(hfac)3 units bridged by the paramagnetic ligands by the means of coordination of their nitronyl nitroxide groups and imidazole rings. Interestingly, each Ln ion is either bound to two nitronyl nitroxide groups or to two imidazole units, and the different Ln centers alternate along the chain. Magnetic studies show that complex 3 exhibits a single-chain magnet behavior.  相似文献   

7.
Herein, we discuss how, why, and when cascade complexation reactions produce stable, mononuclear, luminescent ternary complexes, by considering the binding of hexafluoroacetylacetonate anions (hfac?) and neutral, semi‐rigid, tridentate 2,6‐bis(benzimidazol‐2‐yl)pyridine ligands ( Lk ) to trivalent lanthanide atoms (LnIII). The solid‐state structures of [Ln( Lk )(hfac)3] (Ln=La, Eu, Lu) showed that [Ln(hfac)3] behaved as a neutral six‐coordinate lanthanide carrier with remarkable properties: 1) the strong cohesion between the trivalent cation and the didentate hfac anions prevented salt dissociation; 2) the electron‐withdrawing trifluoromethyl substituents limited charge‐neutralization and favored cascade complexation with Lk ; 3) nine‐coordination was preserved for [Ln( Lk )(hfac)3] for the complete lanthanide series, whilst a counterintuitive trend showed that the complexes formed with the smaller lanthanide elements were destabilized. Thermodynamic and NMR spectroscopic studies in solution confirmed that these characteristics were retained for solvated molecules, but the operation of concerted anion/ligand transfers with the larger cations induced subtle structural variations. Combined with the strong red photoluminescence of [Eu( Lk )(hfac)3], the ternary system LnIII/hfac?/ Lk is a promising candidate for the planned metal‐loading of preformed multi‐tridentate polymers.  相似文献   

8.
The kinetics and mechanism of ligand substitution reaction of coordinated water in complex, [Ru(CN)5H2O]3? by two incoming naphthalene substituted ligands [Ln], that is, Ln = nitroso-R-salt (NRS) and α-nitroso-β-naphthol (αNβN) have been studied spectrophotometrically by following an increase in absorbance at λmax = 525 nm in aqueous medium in presence of anionic surfactant micelle, sodium dodecyl sulphate (SDS) at 25.0 ± 0.1°C as a function of pH, [nitro-R-salt], [α-nitroso-β-naphthol], [Ru(CN)5H2O3?], [SDS] and ionic strength(I) under pseudo-first-order conditions by taking excess [L]. The values of pseudo-first-order rate constants (kobs) were evaluated from the slope of ln(A ? At) versus time plots for each variation. Both systems were found to follow a dissociative mechanism (D), through the formation of an intermediate, [Ru(CN)5]3?. The activation parameters, that is, enthalpy of activation (ΔH) and entropy of activation (ΔS) were computed from the slope and intercept of ln(kf/T) versus (1/T) plot, which support the proposed mechanistic scheme.  相似文献   

9.
Amidoxime modified hydroxypropyl methylcellulose (HPMC) films (HPMC-g-AO) were used for the recovery of uranium from aqueous solutions by a complexation process. The adsorption experiments were carried out by immersion of a certain amount of films in UO2 2+ solutions (resultant pH 4.1) ranging in concentration from 100 to 1,000 ppm. The effect of temperature (25–50 °C) on the adsorption capacity of HPMC-g-AO was investigated at the optimized time. The adsorption kinetics and the thermodynamics as well as the adsorption capacity of HPMC-g-AO films were investigated. The adsorption capacity was found as 765 mg UO2 2+/g dry film. The kinetic and the thermodynamic parameters (i.e. activation energy, enthalpy, entropy and Gibbs free energy) for the interaction of UO2 2+ with HPMC-g-AO were calculated based on known basic relations. The results showed that adsorption occurred through strong electrostatic interactions with an enthalpy of ?36.5 kJ/mol. The desorption of UO2 2+ were investigated using different desorption agents such as EDTA, HCl, NaHCO3, and NaOH. After the 2 weeks treatment period, the highest desorption yield were found as 23 % with NaHCO3.  相似文献   

10.
选用1,2-二苯氧基乙烷取代的氮氧双自由基(BNPhOEt)与稀土金属反应,得到了2例氮氧双自由基-稀土配合物[Ln(hfac)3(BNPhOEt)]·C6H14(Ln=Tb(1)、Ho(2);hfac=六氟乙酰丙酮),其均为2p-4f一维链状结构。磁性研究表明,在配合物12中分别存在铁磁和反铁磁耦合。此外,对2个配合物的荧光光谱进行了研究分析。  相似文献   

11.
Micellisation of sodium dodecyl sulphate (SDS) was studied in the presence of hydrochloric acid (HCl) and perchloric acid (HClO4) using conductometry method. The conductivity-[SDS] plots showed abnormal profile pattern at [HCl] > 0.002 mol dm?3 and [HClO4] > 0.001 mol dm?3. Below these acid concentrations, conductivity pattern was normal, and the critical micelle concentration (CMC) values of SDS were lower in both acids than in water. At high acid concentrations, post-micellar slopes were negative. Fourier transform infrared (FTIR) analysis showed significant shifts in the bands suggesting the formation of dodecyl hydrogen sulphate by SDS at high acid concentrations. Thermodynamic parameters for SDS micellisation at low acid concentrations ([HCl] = 0.002 mol dm?3 and [HClO4] = 0.001 mol dm?3) were determined in the temperature range 15–40°C. As temperature increases, the change in enthalpy and entropy of micellisation becomes less positive, and the change in free energy of micellisation becomes increasingly negative.  相似文献   

12.
Two types of 4f–3d thiostannates with general formula [Hen]2[Ln(en)4(CuSn3S9)] ? 0.5 en ( Ln1 ; Ln=La, 1 ; Ce, 2 ) and [Hen]4[Ln(en)4]2[Cu6Sn6S20] ? 3 en ( Ln2 ; Ln=Nd, 3 ; Gd, 4 ; Er, 5 ) were prepared by reactions of Ln2O3, Cu, Sn, and S in ethylenediamine (en) under solvothermal conditions between 160 and 190 °C. However, reactions performed in the range from 120 to 140 °C resulted in crystallization of [Sn2S6]4? compounds and CuS powder. In 1 and 2 , three SnS4 tetrahedra and one CuS3 triangle are joined by sharing sulfur atoms to form a novel [CuSn3S9]5? cluster that coordinates to the Ln3+ ion of [Ln(en)4]3+ (Ln=La, Ce) as a monodentate ligand. The [CuSn3S9]5? unit is the first thio‐based heterometallic adamantane‐like cluster coordinating to a lanthanide center. In 3 – 5 , six SnS4 tetrahedra and six CuS3 triangles are connected by sharing common sulfur atoms to form the ternary [Cu6Sn6S20]10? cluster, in which a Cu6 core is enclosed by two Sn3S10 fragments. The topological structure of the novel Cu6 core can be regarded as two Cu4 tetrahedra joined by a common edge. The Ln3+ ions in Ln1 and Ln2 are in nine‐ and eightfold coordination, respectively, which leads to the formation of the [CuSn3S9]5? and [Cu6Sn6S20]10? clusters under identical synthetic conditions. The syntheses of Ln1 and Ln2 show the influence of the lanthanide contraction on the quaternary Ln/Cu/Sn/S system in ethylenediamine. Compounds 1 – 5 exhibit bandgaps in the range of 2.09–2.48 eV depending on the two different types of clusters in the compounds. Compounds 1 , 3 , and 4 lost their organic components in the temperature range of 110–350 °C by multistep processes.  相似文献   

13.
Three new lanthanide compounds were obtained using 2-(3-methylthiophene)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) (NIT-3Methien). These compounds, [Gd(hfac)3(NIT-3Methien)2]?0.5CH3(CH2)5CH3 (1: Half n-heptane trihexafluoroacetylacetonate-di-2-(3-methylthiophene)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide gadolinium(III)), [Tb(hfac)3(NIT-3Methien)2]?0.5H2O (2: Half Hydrate trihexafluoroacetylacetonate-di-2-(3-methylthiophene)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide terbium(III)), and [Dy(hfac)3(NIT-3Methien)2]?0.5H2O (3: Half Hydrate trihexafluoroacetylacetonate-di-2-(3-methylthiophene)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide dysprosium(III)), (CH3(CH2)5CH3 = n-heptane), (hfac = hexafluoroacetylacetonate), were characterized structurally and magnetically. The three compounds crystallize in the triclinic space group P1( - ). Ln(III) ion was eight-coordinate by six oxygens from three hfac ligands and two oxygens from two radicals. In 1, direct current (DC) magnetic studies reveal ferromagnetic interactions between the Gd(III) ion and radicals with J1 = 0.94 cm?1. In 2 and 3, there are antiferromagnetic interactions between the Tb(III), or Dy(III) ions and radicals. The luminescence characterizations show that 2 exhibits highly selective luminescent sensing of Cr2O72? ions.  相似文献   

14.
The hydrolytic species of lanthanide ions, La3+ and Sm3+, in water at I = 0.1 mol·dm?3 KCl ionic strength and temperatures of 298.15, 310.15 and 318.15 K were investigated by potentiometry. The hydrolytic species were modeled by the HySS simulation program. From the results, the hydrolytic species of each metal ion at different temperatures were calculated using the program HYPERQUAD2013. The hydrolysis constants (log10 β) of [La(OH)]2+ and La(OH)3 were calculated as ?8.52 ± 0.46, ?26.84 ± 0.48, and log10 β values of [Sm(OH)]2+, [Sm(OH)2]+, Sm(OH)3 were calculated as ?7.11 ± 0.21, ?15.84 ± 0.25 and ?23.44 ± 0.52 in aqueous media at 298.15 K, respectively. The dependence of the hydrolysis constants on the temperature allowed us to calculate the enthalpy, entropy, and Gibbs energy of hydrolysis values of each species.  相似文献   

15.
Activated carbon was prepared from lignocellulosic material (Eucalyptus Globulus labill seed) by chemical activation with ZnCl2 at two different concentrations (10 and 25 % m/v) named ACS25 and ACS10. The textural characteristics of the activated carbons (ACs) were determined by N2 adsorption isotherms; these exhibit B.E.T. surface areas of 250 and 300 m2 g?1 for ACS25 and ACS10, respectively, with micropore volume contents of 0.140 and 0.125 cm3 g?1 in the same order. In addition, the FTIR and Boehm methods were conducted for the chemical characterisation of ACs, where many groups with basic character were found, which favours the adsorption of phenols. The prepared carbonaceous adsorbents were used in the adsorption of wide pollutants monosubstituted phenol derivatives: phenol, 4-nitrophenol and 4-chlorophenol. The effect of temperature on the thermodynamics, kinetic and equilibrium of phenols adsorption on ACs was thoroughly examined. The adsorption kinetics adjusted properly for a pseudo-second-order kinetic model. However, the Elovich model (chemisorption) confirms that phenols adsorption did not occur via the sharing of electrons between the phenolic ring and basal plane of ACs because is not properly adjusted, so the process is given by physisorption. The thermodynamic parameters [i.e. Gibbs free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°)] were also evaluated. The overall adsorption process was exothermic and spontaneous in nature. The values found in the thermodynamic study, confirm that the adsorption process corresponds to a clearly physical process.  相似文献   

16.
The solubilities of sulfadiazine (SD), sulfamerazine (SMR) and sulfamethazine (SMT) in some 1-propanol + water co-solvent mixtures were measured at five temperatures from 293.15 to 313.15 K over the polarity range provided by the aqueous solvent mixtures. The mole fraction solubility of all these sulfonamides was maximal in the 0.80 mass fraction of 1-propanol solvent mixture (δ solv = 28.3 MPa1/2) and minimal in water (δ = 47.8 MPa1/2) at all temperatures studied. The apparent thermodynamic functions Gibbs energy, enthalpy, and entropy of solution were obtained from these solubility data by using the van’t Hoff and Gibbs equations. Apparent thermodynamic quantities of mixing were also calculated by using the ideal solubilities reported in the literature. Nonlinear enthalpy–entropy relationships were observed for these drugs in the plots of enthalpy versus Gibbs energy of mixing. The plot of ?mix H° versus ?mix G° shows different trends according to the slopes obtained when the mixture compositions change. Accordingly, the mechanism for the solution process of SD and SMT in water-rich mixtures is enthalpy driven, whereas it is entropy driven for SMR. In a different way, in 1-propanol-rich mixtures the mechanism is enthalpy driven for SD and SMR and entropy driven for SMT. Ultimately, in almost all of the intermediate compositions, the mechanism is enthalpy driven. Nevertheless, the molecular events involved in the solution processes remain unclear.  相似文献   

17.
Two new lanthanide–radical complexes, [Tb(hfac)3(EtVNIT)2] (1) and [Dy(hfac)3(EtVNIT)2] (2) (EtVNIT?=?2-(4′-ethoxy-3′-methoxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, hfac?=?1,1,1,5,5,5-hexafluoroacetylacetonate), were synthesized; both display radical–Ln(III)–radical (Ln=Tb (1), Dy (2)) tri-spin structures. Magnetic studies reveal that interactions between the lanthanide ions and radicals are ferromagnetic.  相似文献   

18.
Employing nitronyl nitroxide lanthanide(III) complexes as metallo‐ligands allowed the efficient and highly selective preparation of three series of unprecedented hetero‐tri‐spin (Cu?Ln‐radical) one‐dimensional compounds. These 2p–3d–4f spin systems, namely [Ln3Cu(hfac)11(NitPhOAll)4] (LnIII=Gd 1Gd , Tb 1Tb , Dy 1Dy ; NitPhOAll=2‐(4′‐allyloxyphenyl)‐4,4,5,5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide), [Ln3Cu(hfac)11(NitPhOPr)4] (LnIII=Gd 2Gd , Tb 2Tb , Dy 2Dy , Ho 2Ho , Yb 2Yb ; NitPhOPr=2‐(4′‐propoxyphenyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide) and [Ln3Cu(hfac)11(NitPhOBz)4] (LnIII=Gd 3Gd , Tb 3Tb , Dy 3Dy ; NitPhOBz=2‐(4′‐benzyloxyphenyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide) involve O‐bound nitronyl nitroxide radicals as bridging ligands in chain structures with a [Cu‐Nit‐Ln‐Nit‐Ln‐Nit‐Ln‐Nit] repeating unit. The dc magnetic studies show that ferromagnetic metal–radical interactions take place in these hetero‐tri‐spin chain complexes, these and the next‐neighbor interactions have been quantified for the Gd derivatives. Complexes 1Tb and 2Tb exhibit frequency dependence of ac magnetic susceptibilities, indicating single‐chain magnet behavior.  相似文献   

19.
Thiacalix[4]arene contains a circular array of four equivalent hydrogen bonds on its lower rim. The array undergoes a flip–flop motion between two possible directions. The rate of this motion in the temperature range 223–313 K is assessed by means of measurements of the nuclear spin relaxation. The values of the activation enthalpy (38.7 kJ mol? 1) and of the activation entropy ( ? 15 J mol? 1 K? 1) were determined. In addition, correlation times of molecular tumbling have been determined in the same temperature range. The measured properties of thiacalix[4]arene are compared to those of the “classical” calix[4]arene in order to utilize them for fine tuning of the building blocks in supramolecular chemistry.  相似文献   

20.
Third generation poly(amido)amine (PAMAM) dendron was grown on the surface of styrene divinylbenzene (SDB) by divergent polymerization method. This new chelating resin (PAMAMG3-SDB) has been investigated in liquid–solid extraction of thorium. The effects of analytical parameters such as pH, contact time, concentration of thorium, resin dose and temperature on adsorption were investigated. Kinetic and isotherm studies of the adsorption were also carried out to understand the nature of adsorption of thorium on the chelating resin. Kinetic data followed a pseudo-second-order model and equilibrium data were best fitted with Langmuir model. The maximum adsorption capacity of thorium ions was determined to be 36.2 mg g?1 at 298 K. Thermodynamic parameters such as standard enthalpy, entropy, and free energy of adsorption of thorium on PAMAMG3-SDB were calculated as ?10.498 kJ mol?1, 0.0493 kJ mol?1 K?1 and ?25.208 kJ mol?1 respectively at 298 K from temperature dependent equilibrium data.  相似文献   

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