Theoretical predictions of the nitrogen heterocyclic compounds with metal and noble gas (metal = Cu,Ag, Au)

Here, we report a new type of Ng-containing compounds formed between the Ng-M group and nitrogen heterocyclic compounds, (CH₂)_nHNCuNg⁺ (n = 2, 3), (CH)₄NMNg, and (CH)₅NCuNg⁺ (M = Cu, Ag, Au; Ng = Ar, Kr, Xe). Quantum chemistry computations were carried out to optimize their geometric structures and calculate the dissociation energies, dissociation enthalpy, and dissociation free energy change. The stability of these Ng-bonding complexes was inspected by investigating the three dissociation processes of the these compounds into (a) Ng, M, and nitrogen heterocycle C_nN; (b) C_nN + MNg⁺; and (c) C_nNM + Ng, which are all endothermic and nonspontaneous, these dissociation processes are also turned out to be endergonic in nature at standard state. The natural bond orbital, atoms in molecules, and energy decomposition analysis based on the molecular wavefunction show that the M-Ng and M-N bonds have some covalent and electrostatic characters.     

Charge transfer adducts of metal complexes of π-donor ligands with I2 and TCNQ

Copper(II) and nickel(II) biguanides and O-alkyl-1-amidinourea can act as donors for the formation of charge transfer (CT) adducts with I₂ and tetracyanoquinodimethane (TNCQ) as acceptors. Iodine adducts are characterized both in solid and solution states whereas TCNQ adducts obtain only in solution. Appearance of a broad band at 355 nm for iodine adducts and at 335 nm for TNCQ adducts and shifting of i.r. frequencies support the formation of donor acceptor associates. Elemental analysis establishes 1:1 stoichiometry of the solid adducts. The K and ε values determined by modified Benesi—Hildebrand, Scott and Rose—Drago equations are found to be of the order of 10⁴ and 10³ respectively at 298 K in methanol. The solvent effect on the K values is discussed in terms of coupled solute-solute and solute-solvent equilibria.     

Structures,electronic and magnetic properties of the FemOn@Cx (m = 1–3, n = 1–4, x = 50, 60) clusters

The structures, electronic and magnetic properties of the Fe_mO_n@C_x (m?=?1–3, n?=?1–4, x?=?50, 60) clusters have been investigated by using PBE functional. The C₅₀, C₆₀ can significantly increase the structural stabilities of the Fe_mO_n molecules. Fe₂O₃@C₅₀ and Fe₃O₄@C₅₀ are more chemically stable than the Fe₂O₃@C₆₀ and Fe₃O₄@C₆₀ while FeO@C₆₀ is more chemically stable than the FeO@C₅₀. The spin densities of the Fe_mO_n fragments degenerate to zero. Carbon encapsulation leads to the internal charges of the Fe_mO_n fragments transfer from 4 s to 4p orbital.

     

Syntheses,structures, and properties of transition metal complexes with 2-( n -pyridyl)benzimidazole ( n = 2, 3, and 4)

Three pyridylbenzimidazoles (2-PBIM, 3-PBIM, and 4-PBIM) have been prepared (2-PBIM: 2-(2-pyridyl)-benzimidazole, 3-PBIM: 2-(3-pyridyl)-benzimidazole, 4-PBIM: 2-(4-pyridyl)-benzimidazole). Reactions of several transition metals (Cd²⁺, Cu²⁺, Fe²⁺) with the three ligands gave four new coordination complexes, [(Cd)₂(2-PBIM)₂(CH₃COO)₄] (1), [Cu(3-PBIM)₂(CH₃COO)₂]?·?2H₂O (2), [Cu(4-PBIM)₂(CH₃COO)₂(H₂O)]?·?H₂O (3), and [Fe(4-PBIM)₂(Cl)₂(H₂O)₂] (4), respectively. These four complexes have been characterized by X-ray crystallography, IR spectroscopy, and UV absorption spectroscopy. Thermogravimetric properties of 2 and 4 were also measured. X-ray crystallographic studies reveal that these four complexes are very different, although the ligands are similar in structure. The role of hydrogen-bonding and π–π interactions in extending dimensionality of simple complexes has been discussed.     

Synthesis,crystal structures,thermal, and spectroscopic properties of four new metal(II) (M = Co,Ni, Cu,Hg) complexes of 2-benzoylbenzoate with 3-picoline

Four 2-benzoylbenzoate (bba) complexes, [Co(bba)₂(H₂O)₂(3-pic)₂] (1), [Ni(bba)₂(H₂O)₂(3-pic)₂] (2), [Cu(bba)₂(3-pic)₂] (3), and [Hg(bba)₂(3-pic)₂] (4), have been synthesized and characterized by IR spectra, thermal (TG, DTG, and DTA) analysis, and single crystal X-ray diffraction. All the complexes consist of neutral monomeric units with 1 and 2 crystallizing in the orthorhombic (P n a 2₁), 3 in triclinic (P 1), and 4 in monoclinic (P2₁/c) crystal systems. The metal(II) ions exhibit distorted octahedral coordination for 1, 2, and 3 and mercury(II) exhibits distorted trigonal prism coordination. In 1 and 2, bba is monodentate, whereas in 3 and 4 bba is bidentate. 3-Picoline (3-pic) is a classical N-monodentate ligand. Bba are coordinated to metal(II) with carboxylates and IR spectra of all complexes display characteristic absorptions of carboxylate {υ(OCO)_asym and υ(OCO)_sym}. Thermogravimetric (TG) analyses show that 1 and 2 are thermally stable (T_decomp.?>?60°C) and 3 and 4 are thermally stable (T_{decomp .} ?>?120°C).     

Mechanochemical synthesis,structure, and properties of solid solutions of alkaline earth metal fluorides: Ma1−xMbxF2 (M: Ca,Sr, Ba)

The capability of mechanochemical synthesis for the formation of solid solutions of alkaline earth metal fluorides M^a_1−xM^b_xF₂ (M: Ca, Sr, Ba) was tested by fluorination of metal acetates and metal hydroxides with ammonium fluoride directly at milling. Evidence was found for a mutual substitution of cations on their lattice positions in Ca_1−xSr_xF₂ and Ba_1−xSr_xF₂ samples. For the Ba/Ca-system this synthesis route is only partially successful. X-ray diffraction and ¹⁹F MAS NMR spectroscopy were used to characterize all samples concerning their crystal structure and local fluorine coordination. Calculations of ¹⁹F chemical shifts with the superposition model along with probability calculations for the intensity of the individual ¹⁹F lines, performed in dependence on the molar composition of the samples, perfectly agree with the experimental findings. The fluoride ion conductivity of as-prepared samples, determined by temperature dependent DC conductivity measurements, is significantly higher than those of crystalline binary fluorides. Moreover, a higher F⁻ ion conductivity is observed for samples with higher mixing grade in the Ca/Sr-and the Ba/Sr-systems.     

Effect of sintering temperature on electrochemical performance of porous SrTi1-xFexO3-δ (x = 0.35, 0.5, 0.7) oxygen electrodes for solid oxide cells

This work evaluates the effects of the sintering temperature (800 °C, 900 °C, 1000 °C) of SrTi_1-xFe_xO_3-δ (x = 0.35, 0.5, 0.7) porous electrodes on their electrochemical performance as potential oxygen electrode materials of solid oxide cells. The materials were prepared by a solid-state reaction method and revealed the expected cubic perovskite structure. After milling, the powders were characterised by a sub-micrometre particle size with high sinter-activity. It was shown that the lowest area specific resistance was achieved after sintering SrTi_0.65Fe_0.35O₃ electrodes at 1000 °C, and SrTi_0.5Fe_0.5O₃ and SrTi_0.30Fe_0.70O₃ electrodes at 800 °C, which can be considered to be a relatively low temperature. In general, EIS measurements showed that increasing the Fe content results in lowered electrode polarisation and a decrease of the series resistance. Even though the studied materials have much lower total conductivities than state-of-the-art electrode materials (e.g. (La,Sr)(Co,Fe)O₃), the polarisation resistances obtained in this work can be considered low.

     

Synthesis, characterization, and antifungal studies of transition metal complexes of ω-bromoacetoacetanilide isonicotinylhydrazone

Isonicotinic acid hydrazide or isonicotinylhydrazide, commonly known as isoniazid, is an antibacterial agent that has been used to treat tuberculosis. It interacts with microbial cell walls. Schiff’s bases or anils are the compounds having >C=N−N< linkages, which have immense applications as catalysts, stabilizers, pigments, dyes, and drugs. They have good ability to form chelates with many metal ions. Isoniazid can form Schiff’s bases with diketones such as acetoacetanilide. Acetoacetanilide isonicotinylhydrazone and its metal chelates exhibit anticancer activity. Our studies on N-methyl-acetoacetanilide isonicotinylhydrazone and its metal chelates revealed that they are active against pathogenic fungal strains. Hence, it is worthwhile to synthesize new complexes of ligands having different substituents on the acetoacetanilide moiety. We synthesized five new metal chelates of ω-bromoacetoacetanilide isonicotinylhydrazone. The ligand behaved as a tridentate monoanion or as a tridentate dianion in the complexes. These compounds were characterized mainly by elemental analysis; conductivity measurements; and electronic, infrared, and nuclear magnetic resonance spectral studies. We also carried out antifungal studies of these compounds against four selected pathogenic fungal strains using a cup-plate technique. Both the ligand and its metal chelates were active against all fungal strains investigated. However, the chelates were found to be more active than the ligand.     

Fluorescence characterization of metal ion–humic acid interactions in soils amended with composted municipal solid wastes

Fluorescence spectroscopy has been used to probe the structural properties and Cu(II), Zn(II), Cd(II), and Pb(II)-binding behavior of humic acid (HA)-like fractions isolated from a municipal solid waste compost (MSWC) and HAs from unamended and MSWC-amended soils. The main feature of the fluorescence spectra, in the form of emission-excitation matrix (EEM) plots, was a broad peak with the maximum centered at an excitation/emission wavelength pair that was much shorter (340/437 nm) for MSWC-HA than for unamended and MSWC-amended soil HAs (455/513 and 455/512 nm, respectively). Fluorescence intensity for MSWC-amended soil HA was less than that for unamended soil HA. These results were indicative of more aromatic ring polycondensation and humification of soil HAs, and of partial incorporation of simple and low-humified components of MSWC-HA into native soil HA, as a result of MSWC amendment. Titrations of HAs with Cu(II), Zn(II), Cd(II), and Pb(II) ions at pH 6 and ionic strength 0.1 mol L⁻¹ resulted in a marked decrease of the fluorescence intensities of untreated HAs. By successfully fitting a single-site fluorescence-quenching model to titration data, the metal ion complexing capacities of each HA and the stability constants of metal ion-HA complexes were obtained. The binding capacities and stability constants of MSWC-HA were smaller than those of the unamended soil HA. Application of MSWC to soil slightly reduced the metal-ion-binding capacities and affinities of soil HAs.     

Polar interaction of polymer host–solvent enables stable solid electrolyte interphase in composite lithium metal anodes

The lithium(Li) metal anode is an integral component in an emerging high-energy-density rechargeable battery.A composite Li anode with a three-dimensional(3 D) host exhibits unique advantages in suppressing Li dendrites and maintaining dimensional stability.However,the fundamental understanding and regulation of solid electrolyte interphase(SEI),which directly dictates the behavior of Li plating/stripping,are rarely researched in composite Li metal anodes.Herein,the interaction between a polar p...     

Density functional theory study of the adsorption of NO on CunX (n = 2–8; X = Cu,K) clusters

Density functional theory calculations are performed to analyze the structure and stability of Cu and Cu-K clusters with 3 to 9 atoms. The results indicate that the stability of the clusters decreases after doping with a K atom. With the increase of cluster size, the stability of the clusters shows odd-even alternation. Cu₈ and Cu₇K clusters exhibit the highest stability. Next, different adsorption sites are considered to investigate the geometry of Cu_nNO and Cu_n−1KNO clusters. By calculating the adsorption energy and the HOMO-LUMO energy gap, it is determined that both types of reactions are exothermic processes, indicating stable adsorption of NO. Notably, the Cu_nK clusters are more active (stronger adsorption) for NO than the Cu_n clusters. The most chemically active clusters among Cu_nNO and Cu_n−1KNO clusters are Cu₈NO and Cu₇KNO clusters. Finally, electron transfer and Mayer bond order analysis of Cu₈NO and Cu₇KNO clusters reveal that the N O bond order decreases due to electron transfer when Cu/Cu-K clusters adsorb NO. In this process, the N atom is the electron donor and the Cu atom is the electron acceptor. Fundamental insights obtained in this study can be useful in the design of Cu/Cu-K catalysts.     

Thermal behaviour of some metal complexes of N,N-diethyl-N′-benzoyl thiourea

The thermal behaviour of the complexes of N,N-diethyl-N-benzoylthiourea (DEBT) with Ni(II), Cu(II), Pt(II), Pd(II) and Ru(III) was studied using differential thermal analysis (DTA) and thermogravimetry (TG). These complexes undergo only a pyrolytic decomposition process. A gas chromatography-mass spectrometry combined system was used for the verification of the first decomposition product and X-ray diffraction method for the characterization of the final products of pyrolysis.This work was partially supported by Erciyes University Fund Project (AFP 94).     

Synthesis of α,ω-dichloropermethyloligosilanes by reactions of polydimethylsilane with metal chlorides

The reactions of high-molecular-weight polydimethylsilane with metal chlorides in variable oxidation states at high temperature in the absence of a solvent afford mixtures of ,-dichloropermethyloligosilanes Cl(Me₂Si) _m Cl (m= 2—9). The influence of the reaction conditions (temperature, reaction time, and the reagent ratio) on the composition and yields of the reaction products was examined.     

Syntheses and structures of metal–metal triply bonded M2R6 compounds: consideration of starting materials,stability, and structural parameters

The syntheses and structures of four homoleptic metal–metal triply-bonded M₂R₆ compounds [Mo₂(CH₂CMe₂Ph)₆, 1; Mo₂(CH₂SiMe₂Ph)₆, 2; W₂(CH₂SiMe₂Ph)₆, 3; and W₂(CH₂Ph)₆, 4] are reported. The synthetic effort suggests that ditungsten compounds are inherently more difficult to prepare and more thermally sensitive than dimolybdenum compounds, probably as a result of the larger dimetal core the ligands must protect. The structural data confirm that dimetal hexaalkyls exhibit shorter M≡M distances than do dimetal hexaalkoxides, even in a matched pair case where steric differences are minimal.     

Theoretical study of group 11 metal–silonyl complexes: M–SiO and M–(SiO)2 (M = Cu, Ag, or Au)

 The spectroscopic properties of M–SiO and M–(SiO)₂ (1–1 and 1–2 complexes with M = Cu, Ag, or Au) have been theoretically studied. It has been shown that both M–SiO and M–(SiO)₂ compounds in their ground state are bent with a metal–Si bonded structure. The calculated M(ns) spin density agrees well with the electron spin resonance experimental data. From a topological analysis, it has been shown that a rather large charge transfer occurs from the metal towards the SiO moiety, and that the M–Si bond energy correlates with the electron density located at the M–Si bond path (bond critical point). Received: 6 July 2000 / Accepted: 11 October 2000 / Published online: 19 January 2001     

DFT study of chemical mechanism of pre-SERS spectra in Pyrazine–metal complex and metal–Pyrazine–metal junction

The chemical mechanism of Normal Raman Scattering (NRS) and pre-surface enhanced Raman scattering (pre-SERS) spectra for Pyrazine–Ag₂ complex, Ag₂–Pyrazine–Ag₂ junction and Ag₂–Pyrazine–Au₂ junction were investigated with density functional theory (DFT) and charge difference densities (CDDs) for the first time. The NRS intensities of the above three structures enhanced obviously relative to isolated Pyrazine and the enhancement mechanism was confirmed to be static chemical enhancement. The pre-SERS intensities of the above three structures enhanced evidently compared to corresponding NRS intensities, and the enhancement mechanism was confirmed to charge transfer (CT) resonance Raman enhancement. The largest enhanced orders of NRS and pre-SERS intensities among the three structures were up to 10³ and 10⁵, respectively. Compared the intensity of pre-SERS with corresponding intensity of NRS spectra, the enhancement effect of Pyrazine–Ag₂ complex was larger than the others. Intramolecular and intermolecular CT on resonant electronic transition were described by CDDs.     

Separation of metal ions by capillary electrophoresis – diversity, advantages, and drawbacks of detection methods

Capillary electrophoresis (CE) has been applied to metal-ion analysis during the last 10 years. To improve sensitivity and selectivity different modes of detection have been adapted or developed. The selection of commercially available detection systems for metal-ion analysis is still primarily limited to UV–Vis detection, although other commercial systems, e.g. fluorescence, conductivity, or interfaces for coupling to mass spectrometry (MS) or inductively coupled plasma mass spectrometry (ICP–MS) are becoming available. High demands are made on any detector used in CE, because the analytical signal has to be extracted from less than 1 nL of sample, which corresponds to a total amount of ≤ 10^–12 to 10^–15 mol analyte. This paper compares currently available and recently developed detection methods for CE as applied to the analysis of metal ions. Commercially available techniques, for example UV– Vis, fluorescence, or mass spectrometry, and other new detection methods including electrochemistry, radioactivity, and XRF, are discussed and future trends are anticipated.     

Synthesis,characterization, and antimicrobial activities of barbital-based alkaline earth metal complexes: the X-ray crystal structure of [Ba2H(Barb)5] (Barb = 5,5-diethyl barbiturate)

Three barbital-based alkaline earth metal complexes, [Ca(Barb)₂]?·?3H₂O (1), [Ba₂H(Barb)₅] (2) and [Mg(Barb)₂]?·?2H₂O (3) (Barb?=?5,5-diethyl barbiturate sodium salt), were synthesized and characterized with elemental analysis, thermal analysis, and infrared, Raman, ultraviolet, and NMR (¹H and ¹³C) spectroscopies. Single-crystal X-ray diffraction studies reveal that 2 is a dimer. Each barium(II) is surrounded by an O₇N₂ donor set in an approximate monocapped square antiprism with Ba–O distances ranging from 2.6512(14) to 2.9168(15)?Å and Ba–N distances of 2.7601(15) and 3.2558(17)?Å. The complex forms polymeric networks in the solid state with different coordinating abilities of O and N donors and N–H···O hydrogen bonds. The antimicrobial activities of 1–3 were observed against different gram-positive and gram-negative bacteria, yeast, and molds. Variable antimicrobial activity against the different bacteria strains was observed and compared with that of standard antibiotics; minimum inhibitory concentration values ranged from 22 to 170?µg?mL^?1 for bacteria.     

Syntheses, structures, and properties of metal complexes involving π-conjugated tetrathiafulvalene-pyridine ligand

Four metal complexes based on the phenyl-bridged pyridine ligand with tetrathiafulvalene unit (TTF-Ph-Py, L), Ni^II(acac)₂(L)₂ (1, acac = acetylacetonate), M(hfac)₂(L)₂ (M = Ni^II, 2; M = Cu^II, 3; hfac = hexafluoroacetylacetonato) and [Co^II(Tp^Ph2)(OAc)(L)]·H₂O (4, Tp^Ph2 = hydridotri(3,5-diphenylpyrazol-1-yl) borate), have been synthesized and structurally characterized. The absorption spectra and redox behaviors of these new compounds have been studied. Optimized conformation and molecular orbital diagram of L has been calculated with density functional theory (DFT).