An Infrared Spectroscopic Study on the Hofmann-diam-type 1,12-Diaminododecanemetal(II) Tetracyanonickelate(II)-aromatic Guest Clathrates: M(H2N(CH2)12NH2)Ni(CN)4ċG(M=Co, Ni or Cd; G = Benzene, Naphthalene, Anthracene, Phenanthrene or Biphenyl)

Three Hofmann-diaminododecane-type clathrates of the form M(1,12-diaminododecane) Ni(CN)₄G (M = Co, Ni or Cd; G = benzene, naphthalene, anthracene, phenanthrene or biphenyl) have been prepared in powder form. The 1,12-diaminododecane molecules in the host lattice permit the inclusion of bulky guest molecules. The spectral features suggest that these compounds are similar in structure to the other Hofmann-diam-type clathrates.     

Cyan-Blue Luminescence and Antiferromagnetic Coupling of CN-Bridged Tetranuclear Complex Based on Manganese(III) Schiff Base and Hexacyanoferrate(III)

A new tetranuclear cyanide-bridged Mn^III–Fe^III complex based on manganese(III) Schiff base and hexacyanoferrate(III) units, [Mn(L)(MeOH)₂][{Mn(L)}{Fe(CN)₆}{Mn(L)(MeOH)}].2MeOH, [H₂L?=?N,N′-bis(2-hydroxy-1-naphthalidenato)-1,2-diaminopropane] (1), has been synthesized and characterized by elemental analysis, UV–Vis, FT-IR, PXRD, single crystal X-ray analyses, magnetic and photoluminescence measurements. Complex 1 consist of one trinuclear cyanido-bridged anion, in which [Fe(CN)₆]^3? anion bridge [Mn(L)]⁺ and Mn(L)(MeOH)}]⁺ cations via two C≡N groups in the cis positions, and also one isolated manganese [Mn(L)(MeOH)₂]⁺ cation. DC magnetic susceptibility and magnetization studies showed that complex 1 indicates an antiferromagnetic coupling between low-spin Fe(III) and high-spin Mn(III) through the cyanide bridges. In addition, the complex 1 displays a strong cyan-blue luminescence emission in the solid state condition at room temperature. This behavior might be seen easily from the chromaticity diagram. Thus, the complex may be a good promising cyan-blue OLED developing electroluminescent materials for flatted or curved panel display applications due to the fact that it has such features.     

Online Solid-Phase Extraction of Cd(II), Cu(II), and Co(II) Using Covalently Attached Bis(salicylaldimine) to Silica Gel for Determination in Food and Water by Flame Atomic Absorption Spectrometry

In this study, a novel sorbent material bearing a bis(aldimine) group was designed and successfully synthesized by covalently bonding a 2-[N,N′-bis(salicylaldimine)]aminoethyl amine ligand to the silica gel surface that was characterized by carbon, hydrogen, and nitrogen elemental analysis, thermogravimetric analysis, and the Fourier transform infrared spectroscopy technique. The sorbent was used for the online solid-phase extraction (SPE) of Cd(II), Cu(II), and Co(II) ions for their determination at trace concentration levels by flame atomic absorption spectrometry. The effective factors for the online SPE such as the pH and the flow rate of the sample solution, and type, volume, and flow rate of eluent were investigated. The concentration levels of Cd(II), Cu(II), and Co(II) were measured in certified reference materials including Virginia tobacco leaves (CTA-VTL-2) and water-trace elements (NWTM-15.2) to validate this method. The metal levels in environmental water were determined by this method, and the values were checked by spiking and recovery experiments and independent analysis by inductively coupled plasma-mass spectrometry. The adsorption capacities of the sorbent were found to be 41.2, 31.6, and 25.6?mg/g for Cd(II), Cu(II), and Co(II), respectively. This method was also successfully used for the determination of Cd(II), Cu(II), and Co(II) concentrations in rice and molasses.     

One-pot synthesis of novel 3,10-dihydro-2H-1,3-oxazepino[7,6-b]indoles via 1,4-dipolar cycloaddition reaction

3,10-Dihydro-2H-1,3-oxazepino[7,6-b]indoles are synthesized via a convenient one-pot three-component 1,4-dipolar cycloaddition reaction, involving 3-alkyl(aryl)imidazo[1,5-a]pyridines, dimethyl acetylenedicarboxylate (DMAD) and N-alkylisatins. Structures of the newly synthesized heterocycles are evidenced from spectral data and further confirmed by single crystal X-ray diffraction. A plausible reaction mechanism is advanced, whereby the intermediate 1,4-dipole, generated in situ from imidazo[1,5-a]pyridine and DMAD, initially adds to the keto group of N-alkylisatins to form the corresponding 1,3-oxazin-spiro-oxindole cycloadduct. The latter undergoes subsequent unprecedented skeletal rearrangement through a cascade of bond breaking and bond making processes, eventually leading to ring enlargement, furnishing the tricyclic oxazepino[7,6-b]indole ring system as the end product.     

Chiral 2-(2-hydroxyaryl)alcohols (HAROLs) with a 1,4-diol scaffold as a new family of ligands and organocatalysts

Efficient and modular syntheses of chiral 2-(2-hydroxyaryl)alcohols (HAROLs), novel 1,4-diols carrying one phenolic and one alcohol hydroxyl group, have been developed which led to generation of a small library of structurally diverse HAROLs in enantiomerically pure form. Of the different HAROLs examined, a HAROL based on the indan backbone exhibited the highest activity and enantioselectivity in the 1,2-addition of certain organometallic compounds to aldehydes in the presence of Ti(OⁱPr)₄ (up to 97% y, 88% ee) and performed as a hydrogen-bond donor organocatalyst in the Morita-Baylis-Hillman reaction, promoted by trialkylphosphines.     

Starch coated titanium dioxide nanoparticles as a challenging sorbent to separate and preconcentrate some heavy metals using graphite furnace atomic absorption spectrometry

In this study, a challenging nanosorbent was described for preconcentration/separation method based on the sorption of cadmium, cobalt, copper, nickel, lead on starch coated titanium dioxide nanoparticles and its analysis by graphite furnace atomic absorption spectrometry. Optimum conditions were investigated for quantitative sorption. By using the proposed technique, the analyte elements were determined in spiked tap-water samples in the range of 95% confidence level. Limit of detection (3δ) was 0.05, 0.28, 1.90, 3.10 and 0.11 µg/L (3σ, N = 10) for cadmium, cobalt, copper, nickel and lead, respectively. The optimised technique is fast, easy handled, simple and environmental friendly.     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

Studies on heterocyclic enamines: New syntheses of 4H-pyranes,pyranopyrazoles and pyranopyrimidines

The behaviour of several 2-amino-3-cyano-4H-pyran derivatives toward a variety of nucleophilic reagents is reported.     

Usage of deep eutectic solvents for the digestion and ultrasound-assisted liquid phase microextraction of copper in liver samples

In this study, we used deep eutectic solvents for digestion and ultrasound-assisted emulsification liquid phase microextraction (UA-ELPME) of copper in liver samples. Different types of DESs were prepared for digestion and microextraction steps. DESs consisting of lactic acid and choline chloride for the digestion step and DESs consisting of tetrabuthylamonium chloride and decanoic acid for ultrasound-assisted emulsification liquid phase microextraction were used in this method. The liver samples were digested by using DES-based digestion method. After digestion step, Cu(II) ions in aqueous phase were complexed with sodium dimethyl dithiocarbamate (NaDMDTC) and the obtained hydrophobic complex was extracted to tetrabuthylamonium chloride-decanoic acid DES phase. A microsample injection system coupled with flame atomic absorption spectrometer (MS-FAAS) was used in the detection of copper. LOD, LOQ, PF and % RSD were determined as 4.00, 13.2 µg L^??1, 10 and 3.2%, respectively. The proposed microextraction procedure was successfully applied to copper contents of the liver samples.     

Ni(II), Cu(II), and Zn(II) complexes of tetradentate schiff base containing two thiadiazoles units: Structural,spectroscopic, magnetic properties,and molecular modeling studies

Four new mononuclear metal complexes with a mononucleating Schiff base ligand containing two thiadiazoles units have been synthesized. The ligand and metal complexes were characterized by elemental analyses, IR, ¹H, and ¹³C NMR, UV–vis, ESR, electrospray ionization mass spectra, and magnetic susceptibility measurements. Electronic spectra, magnetic susceptibility measurement, and molecular modeling studies support octahedral geometry around the Ni(II), Cu(II), and Zn(II) ions. The magnetic properties were investigated, and ferromagnetic coupling is observed in Cu(II) and Ni(II) complexes. In addition, total energy and heat of formation calculated for conformers of the Schiff base ligand by the semiempirical AM1 calculations have shown that E,Z‐isomer of the ligand is more stable (about 5.3 kcal/mol) than E,E‐ and Z,Z‐isomers. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:700–712, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20496