Thermal degradation pathways of nickel(II) bipyridine complexes to size-controlled nickel nanoparticles

Tris(bipyridine)nickel(II) chloride (1) and bis(bipyridine)nickel(II) chloride (2) pyrolize at heating rate of 50 °C/min to a maximum of 450 °C for 24 h under an inert atmosphere of flowing argon gas, to yield size-controlled nickel nanoparticles. Thermogravimetric studies of the complexes (1) and (2) and GC–MS analysis of the trapped volatile matter evolved during thermal degradation of the complexes indicate their clean decomposition pathway to zero-valent nickel. Both heating rate and argon gas flow rate affect purity, particle size, and shape of the particles. X-ray powder diffractometry and atomic force microscopy showed the formation of face-centered cubic (fcc) structured nickel particles having particle size in the range of 3.5–5.0 nm. Magnetic susceptibility measurements suggest nickel nanoparticles to be ferromagnetic in nature characterized by particle size–dependent Curie temperature and high coercivity that is comparable to the bulk iron.     

Metallomacrocycles with a Difference: Macrocyclic Complexes with Exocyclic Ruthenium(II)‐Containing Domains

The templated synthesis of organic macrocycles containing rings of up to 96 atoms and three 2,2′‐bipyridine (bpy) units is described. Starting with the bpy‐centred ligands 5,5′‐bis[3‐(1,4‐dioxahept‐6‐enylphenyl)]‐2,2′‐bipyridine and 5,5′‐bis[3‐(1,4,7‐trioxadec‐9‐enylphenyl)]‐2,2′‐bipyridine, we have applied Grubbs’ methodology to couple the terminal alkene units of the coordinated ligands in [FeL₃]²⁺ complexes. Hydrogenation and demetallation of the iron(II)‐containing macrocyclic complexes results in the isolation of large organic macrocycles. The latter bind {Ru(bpy)₂} units to give macrocyclic complexes with exocyclic ruthenium(II)‐containing domains. The complex [Ru(bpy)₂(L)]²⁺ (isolated as the hexafluorophosphate salt), in which L=5,5′‐bis[3‐(1,4,7,10‐tetraoxatridec‐12‐enylphenyl)]‐2,2′‐bipyridine, undergoes intramolecular ring‐closing metathesis to yield a macrocycle which retains the exocyclic {Ru(bpy)₂} unit. The poly(ethyleneoxy) domains in the latter macrocycle readily scavenge sodium ions, as proven by single‐crystal X‐ray diffraction and atomic absorption spectroscopy data for the bulk sample. In addition to the new compounds, a series of model complexes have been fully characterized, and representative single‐crystal X‐ray structural data are presented for iron(II) and ruthenium(II) acyclic and macrocyclic species.     

Synthesis,Magnetic Properties and X‐ray Structure Analysis of a 1‐D Chain Iron(II) Spin Crossover Complex with wide Hysteresis

The reaction of [FeL(MeOH)₂] (L being a tetradentate [N₂O₂]^2? coordinating Schiff base like ligand [([3,3′]‐[1,2‐phenylenebis(iminomethylidyne)]bis(2,4‐pentane‐dionato)(2‐)N,N′,O²,O²′], MeOH = methanol) with 4,4′‐bipyridine (bipy) results in the formation of a new iron(II ) spin crossover coordination polymer of the formula [FeL(bipy)] ( 1 ). T‐dependent susceptibility measurements revealed an abrupt HS ? LS spin transition with an approximately 18 K‐wide thermal hysteresis loop (T_1/2↑ = 237 K and T_1/2↓ = 219 K). The isolation of crystals suitable for X‐ray structure analysis allowed the determination of the motive of the molecule structure of the first 1‐D chain compound with hysteresis in the HS form at 250 K. Despite the low qualtity of the data, we were able to obtain some insight into the interplay of covalent and elastic interactions that are both responsible for the high cooperative interactions during the spin transition in this compound.     

Characterization of Iron Sulfide Species in Model Solutions by Cyclic Voltammetry. Revisiting an Old Problem

A long‐standing problem associated with voltammetric determination of iron and sulfide in reduced natural waters has been the nature of the presumed analyte responsible for a reduction peak at ?1.1 V vs. Ag/AgCl. Cyclic voltammetry at the Hg electrode is used here to study solutions with different Fe(II) to sulfide ratios in chloride and acetate electrolytes (pH 6–7). The results indicate that the ?1.1 V peak can be assigned to reduction of Fe²⁺ or its labile complexes on FeS layers that partially cover the Hg electrode. Hg electrodes covered with FeS act like FeS solid electrodes over a very wide potential range (?0.35 to ?1.9 V). Two mechanisms for forming FeS layers on Hg are described. Over the broadest deposition potential range, the dominant mechanism involves attachment at the Hg surface of FeS nanoparticles, which are generated quickly in initially supersaturated mixtures of Fe(II) and S(–II). In a narrow deposition potential range, roughly ?0.56 to ?0.70, FeS layers are produced additionally by replacement of preformed HgS. Because Fe²⁺ is reduced at ?1.1 V on FeS layers and at ?1.4 V on bare Hg, it may be underdetermined when only the ?1.4 V peak is measured.     

Facile synthesis of superparamagnetic manganese ferrite nanoparticles as a novel T2 MRI contrast agent

With co-precipitation method we successfully synthesized an aqueous dispersible, superparamagnetic manganese ferrite nanoparticles at relatively low temperature (190 ​°C). This material shows potential application as T₂ MRI contrast agent. Cost-effective and less toxic manganese (II) chloride (MnCl₂·4H₂O) and iron (III) chloride hexahydrate (FeCl₃·6H₂O) were used as precursors and 2-[2-(2-Hydroxyethoxy)ethoxy] ethanol (TEG) were utilized as solvent which served as stabilizer and provided a reduction system. The mean diameter of these nanoparticles is about 7 ​nm. Its saturation magnetization (Ms) and relaxivity value (r₂) are as high as 46 emu/g and 593.9 ​mM⁻¹s⁻¹ respectively. In vitro cell study demonstrated pancreatic cancer cells could keep viable when the manganese ferrite nanoparticles concentration reached up to 50 ​μg/mL.     

Chlorination as a means for changing the composition of iron-containing nanoparticles in a polyethylene matrix

Mössbauer spectroscopy, X-ray powder diffraction, and transmission electron microscopy were used to study the reactions of Fe₃O₄ or FeCl₂ · 4H₂O nanoparticles stabilized in a polyethylene (HPPE) matrix with gaseous chlorine and hydrogen chloride. These reactions produce FeCl₂ · 2H₂O nanoparticles, which retain the particle size and distribution over the HPPE matrix intrinsic to precursor nanoparticles. We propose chemical modification of iron-containing nanomaterials as a means for manufacturing iron(II) chloride nanoparticles.     

Calculations of microconstants and equilibrium formation constants for platinum(II) and palladium(II) halide complexes in solution

Distribution diagrams and formation functions for halide complexes [M(H₂O)_{4 ? n} Cl _n ]^{2 ? n} (M = Pt(II) or Pd(II)) and [PdCl_{4 ? n} Br _n ]^2? (n = 0?C4) in solution are analyzed in terms of the matrix model. Equilibrium constants for binding the first ligand $\left( {\bar K} \right)$ and corrections for the mutual influence between ligands (??) in the course of complex formation in solution are calculated. In examples analyzed, the substitution of chloride ion for water in the coordination sphere of platinum(II) and palladium(II) is an anti-cooperative process. The substitution of bromide ion for chloride ion in the coordination sphere of [PdCl₄]^2? is weakly cooperative. Quantum-chemical calculations show that platinum(II) and palladium(II) cis-bisaquadichloro complexes in the gas phase are thermodynamically less stable than trans-isomers. The cis-trans isomerization constants in the gas phase calculated by the DFT method and those found for solutions using the matrix model have the same order of magnitude.     

Removal of Lead(II), Cadmium(II), and Arsenic(III) from Aqueous Solution Using Magnetite Nanoparticles Prepared by Green Synthesis with Box–Behnken Design

Two types of magnetite (Fe₃O₄) nanoparticles were investigated as adsorbents for the simultaneous removal of Pb(II), Cd(II), and As(III) metal ions from aqueous solution. Magnetite nanoparticles were prepared by two synthesis procedures, both using water as solvent, and are referred to as conventional Fe₃O₄ nanoparticles and green Fe₃O₄ nanoparticles. The latter used Citrus limon (lemon) aqueous peel extract as the surfactant. Box–Behnken experimental design was used to investigate the effects of parameters such as initial concentration (20–150?mg?L^?1), pH (2–9), and biomass dosage (1–5?g?L^?1) on the removal of Pb(II), Cd(II), and As(III) ions. The optimum parameters for removal of the studied metal ions from aqueous solutions, including the initial ion concentration (20?mg?L^?1), pH (5.5) and adsorbent dose (5?g?L^?1), were determined. The pseudosecond-order model exhibited the best fit for the kinetic studies, while adsorption equilibrium isotherms were best described by Langmuir and Freundlich models. The optimum conditions were applied for the treatment wastewater. The removal efficiencies of Pb(II), Cd(II), and As(III) using the conventional and green synthesized Fe₃O₄ nanoparticles were 59.4?±?4.3, 18.7?±?1.9 and 17.5?±?1.6, and 98.8?±?5.6, 46.0?±?1.3, and 48.2?±?2.6%, respectively. These results demonstrate the potential of magnetite nanoparticles synthesized using C. limon peel extract as highly efficient adsorbents for the removal of Pb(II), Cd(II), and As(III) ions from aqueous solution.     

Synthesis,Characterizations, Magnetism and Thermal Degradation of a 2‐Fold Interpenetrated 3D Cobalt‐Organic Framework

A new coordination polymer, [Co₂(L)₂(4,4′‐bipy)]_n·3nH₂O ( 1 ) based on 5‐(3‐methyl‐5‐phenyl‐4H‐1,2,4‐triazol‐4‐yl)isophthalic acid (H₂ L ) and 4,4′‐bipyridine (4,4′‐bipy) has been hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction, XRPD, IR, and elemental analysis. Temperature‐dependent magnetic susceptibility and thermal degradation for 1 were also studied. The asymmetric unit of compound 1 consists of two crystallographically independent Co(II) ion, two L ^2? ligand, one 4,4′‐bipy ligand, and three lattice water molecules. The 2D triangle networks were linked by the bridging 4,4′‐bipy ligand to give rise to a 2‐fold interpenetrated 3D architecture. The simplest cyclic motif of the 2D networks is a triangle ring consisting of three Co(II) cations and three L ^2? ligands. So we can define Co(II) ions as 4‐connected nodes and the L ^2? ligands as 3‐connected nodes. Thus, the 3D structure can be described as a 2‐fold parallel interpenetrated ins InS 3,4‐conn topology.     

Synthesis and characterization of copper(II) dithiocarbamate complexes involving pyrrole and ferrocenyl moieties and their utility for sensing anions and preparation of copper sulfide and copper–iron sulfide nanoparticles

Bis(N‐(pyrrol‐2‐ylmethyl)‐N‐butyldithiocarbamato‐S,S′)copper(II) ( 1 ), bis(N‐(pyrrol‐2‐ylmethyl)‐N‐(2‐phenylethyl)dithiocarbamato‐S,S′)copper(II) ( 2 ), bis(N‐methylferrocenyl‐N‐(2‐phenylethyl)dithiocarbamato‐S,S′)copper(II) ( 3 ) and bis(N‐furfuryl‐N‐methylferrocenyldithiocarbamato‐S,S′)copper(II) ( 4 ) were prepared and characterized using elemental analysis and infrared and UV–visible spectroscopies. X‐ray diffraction (XRD) studies on 3 show that each copper centre adopts the square planar geometry by the coordination of four sulfur atoms of the metalloligand N‐methylferrocenyl‐N‐(2‐phenylethyl)dithiocarbamate. The Cu? S distances are symmetrical and are in the range 2.293–2.305 Å. The supramolecular architecture in complex 3 is sustained in the solid state by C? H???π, C? H???S, Fe???Fe and H???H interactions. Density functional theory calculations were carried out for 3 . Anion (F^?, Cl^?, Br^? and I^?) binding studies with complex 1 were performed using cyclic voltammetry. Copper sulfide, copper–iron sulfide‐ 1 and copper–iron sulfide‐ 2 nanoparticles were prepared from complexes 2 , 3 and 4 , respectively, and they were characterized using powder XRD, transmission electron microscopy (TEM) and energy‐dispersive X‐ray, UV–visible, photoluminescence and infrared spectroscopies. TEM images of copper–iron sulfide‐ 1 and copper–iron sulfide‐ 2 reveal that the particles are spherical and oval shaped, respectively. Photocatalytic activities of as‐prepared nanoparticles were studied by decolourization of methylene blue and rhodamine‐B under UV light. It was found that copper–iron sulfide degrades methylene blue and rhodamine‐B much better than does copper sulfide.     

1H NMR assignment corrections and 1H, 13C, 15N NMR coordination shifts structural correlations in Fe(II), Ru(II) and Os(II) cationic complexes with 2,2′‐bipyridine and 1,10‐phenanthroline

¹H, ¹³C and ¹⁵N NMR studies of iron(II), ruthenium(II) and osmium(II) tris‐chelated cationic complexes with 2,2′‐bipyridine and 1,10‐phenanthroline of the general formula [M(LL)₃]²⁺ (M = Fe, Ru, Os; LL = bpy, phen) were performed. Inconsistent literature ¹H signal assignments were corrected. Significant shielding of nitrogen‐adjacent protons [H(6) in bpy, H(2) in phen] and metal‐bonded nitrogens was observed, being enhanced in the series Ru(II) → Os(II) → Fe(II) for ¹H, Fe(II) → Ru(II) → Os(II) for ¹⁵N and bpy → phen for both nuclei. The carbons are deshielded, the effect increasing in the order Ru(II) → Os(II) → Fe(II). Copyright © 2010 John Wiley & Sons, Ltd.     

Determination of microamounts of iron by hydroxamate resin colorimetry

Summary A new, sensitive chelating ion-exchanger colorimetric method has been developed for the determination of iron at the g/l level in water, based on the direct measurement of light absorption of iron hydroxamate resin complex. In 0.2 N perchloric acid solution, iron could be rapidly, selectively and quantitatively absorbed on the hydroxamate resin. The calibration curve for iron(III) of a 25 ml solution was linear in the concentration range 8.00×10^–6 to 5.00×10^–5 M. For iron(III) with larger sample volumes, the relative detection limit was increased. Most of the metals interfered negligibly, such as Ca(II), Co(II), Cu(II), Ni(II) and Zn(II), except for higher concentration of lead(II) and mercury(II) when present at up to 400 times the concentration of iron(III). The effects of EDTA, glycine, thiourea, phosphate, nitrate and chloride on the retention of iron(III) were also examined. Only thiourea significantly influenced the retention of iron(III). The presence of sodium chloride even at a concentration of 3.5×10⁴ times that of iron(III) did not interfere at all.

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Bestimmung von Mikromengen Eisen durch Hydroxamatharz-Colorimetrie

     

Synthesis and characterization of bis(organothiolato)mercury(ii) complexes by disproportionation of Hg2Cl2 in the presence of thiols

Mercury(I) chloride disproportionates to mercury metal and bis(organothiolato)mercury(II) in the presence of some thiols in good yields. The products were analyzed by means of ¹H?NMR and gas chromatographic–mass spectrometry (GC/MS), which indicated that the complexes are monomers in the gas phase and decomposed at elevated temperature to mercury(0) and corresponding disulfides.     

Molecular Solar Thermal Batteries through Combination of Magnetic Nanoparticle Catalysts and Tailored Norbornadiene Photoswitches

Cobalt catalysts are immobilized on the surface of iron oxide nanoparticles for the preparation of highly active quasi-homogeneous catalysts toward an efficient release of photochemically stored energy in norbornadiene-based photoswitches. The facile separation of the iron oxide nanoparticles through exploitation of the intrinsic magnetic properties of this material enables efficient cyclization of energy storage and release. Through the transition from cobalt (II) salphen to cobalt porphyrins, a 22.6-fold increase in the catalytic efficiency of the QC-NBD back-conversion is achieved, with an initial TOF of up to 3.64 s⁻¹ and excellent TON of over 3305. In addition, a series of novel “push–pull” functionalized norbornadiene derivatives is prepared, featuring excellent absorption properties with maxima up to 366 nm, quantum yields around 70 %, high energy storage capacities of up to 98.0 kJ mol⁻¹, and outstanding thermal stability with t_1/2 (25 °C) over 100 days. Finally, the energy storage potential of these molecular solar thermal (MOST) systems is harnessed in a heat release experiment. This demonstrates the potential of norbornadiene-based photoswitches in combination with efficient magnetic catalysts for the generation of environmentally benign process heat.     

Synthesis and characterization of alt‐bipyridinylene‐phenylene copolymers containing ruthenium(II) complexes

Poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3a ), poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐4,4′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3b ), and poly{bis(2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3c ) were synthesized by the Suzuki coupling reaction. The alternating structure of the copolymers was confirmed by ¹H and ¹³C NMR and elemental analysis. The polymers showed, by ultraviolet–visible, the π–π* absorption of the polymer backbone (320–380 nm) and at a lower energy attributed to the d–π* metal‐to‐ligand charge‐transfer absorption (450 nm for linear 3a and 480 nm for angular 3b ). The polymers were characterized by a monomodal molecular weight distribution. The degree of polymerization was approximately 8 for polymer 3b and 28 for polymer 3d . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2911–2919, 2004     

Formation conditions of a magnetically ordered phase ɛ-Fe2O3. A FMR in situ study

The ferromagnetic resonance (FMR) method in situ is used to study the initial stages of the formation of ? iron oxide nanoparticles deposited on silica gel at temperatures up to 600°C. It is shown that at high-temperature treatment of starting samples obtained by impregnation with an iron(II) sulfate solution, supermagnetic ?-Fe₂O₃/SiO₂ nanoparticles form with a narrow size distribution. An analysis of the FMR data in comparison with the data of other methods enables the formulation of the formation conditions for systems of deposited ?-Fe₂O₃ nanoparticles without other polymorph impurities.     

Control of Redox Potential by Deprotonation of Coordinated 1H‐Imidazole in Complexes of 2‐(1H‐Imidazol‐2‐yl)pyridine

Complexes [ML₃]²⁺ of the bidentate ligand 2‐(1H‐imidazol‐2‐yl)pyridine were prepared with iron(II), cobalt(II), and ruthenium(II). The electronic spectra suggest the ligand to be a weaker σ‐donor and π‐acceptor than the closely related 2,2′‐bipyridine. The complexes are readily deprotonated by addition of base, and the effect of the deprotonation is to lower the M^III/M^II redox potential by roughly 900 mV. This is roughly 75% of the drop observed for related complexes of 2,6‐di‐1H‐imidazol‐2‐ylpyridine, and suggests the effect to be largely coulombic in origin.     

A miniaturized flow-injection analysis ( μ FIA) system with on-line chemiluminescence detection for the determination of iron in estuarine water

A miniaturized flow-injection analysis system constructed from a glass base plate and polydimethylsiloxane (PDMS) top plate was employed for the determination of iron in river water. Two designs were investigated, one utilizing a syringe pump and the other utilizing EOF pumping with a mini-filtration system incorporated. The syringe pump system was used to optimize the analytical method on chip, where the pump was used to deliver both the analyte and the reagents to the reactor chip. The highly sensitive chemiluminescence reaction between alkaline luminol (3-aminophthalhydrazide) and 0.1?M of hydrogen peroxide (H₂O₂) in the presence of iron(II) was utilized. The bright blue light (λ _max?～?440?nm) emitted was detected using a miniaturized photomultiplier tube interfaced directly under the chip. The light intensity signals were recorded, and the corresponding concentration of iron(II) concentration was determined. The calibration for iron(II) standards was linear up to 0.75?µg?mL^?1 (y?=?5.7839x?+?0.0378, r² ?=?0.9939) with a precision value of up to 3.72% RSD, for n?=?3. The limits of detection (blank?+?3s _y/x) were found to be 28?ng?mL^?1. The system which utilized EOF pumping and incorporated a minifiltration unit provided a linear calibration for 0–5?µg?mL^?1 (y?=?3.316x?+?0.1831; correlation coefficient, r ²?=?0.9996) over a working range of 0.0–0.5?µg?mL^?1. This system provided lower limits of detection 5.1?ng?mL^?1 and better repeatability (%RSD less than 0.5% for n?=?4), but problems occurred with the mini-filtration system at higher iron(II) concentrations. The EOF pumping system provided slightly higher results for the concentration of iron(II) in the Humber estuary (0.058?µg?mL^?1), but these results were in line with the results expected by the Environment Agency.     

Vacuum balance and related studies of green and red rusts

Green and red rusts are formed when iron is partially or completely oxidised. Analogues of the rusts may be precipitated from iron(II) and iron (III) salt solutions treated with alkali under reducing or oxidising conditions. Variations in surface area and porosity have been investigated by gravimetric nitrogen gas sorption, using vacuum microbalance techniques.Freshly-precipitated red rusts, hydrous iron (III) oxide, have surface areas of about 200–400 m²g^?1. When they are added to iron (II) hydroxide suspensions kept at pH 7, the green Fe (II)-Fe (III) rusts formed have lower surface areas of about 40–100 m²g^?1, depending on the initial iron(II) sulphate concentrations.