Copper(II) azide complexes of aliphatic and aromatic amine based tridentate ligands: novel structure, spectroscopy, and magnetic properties

Copper(II) azide complexes of three tridentate ligands namely 2,6-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L), 2,6-(pyrazol-1-ylmethyl)pyridine (L'), and dipropylenetriamine (dpt) yield three kinds of complexes with different azide-binding modes. The ligand L forms two end-on-end (mu-1,3) diazido-bridged binuclear complexes, [CuL(mu-N(3))](2)(ClO(4))(2) (1) and [CuL(mu-N(3))(ClO(4))](2).2CH(3)CN (2), and L' forms a perchlorato-bridged quasi-one-dimensional chain complex, [CuL'(N(3))(ClO(4))](n)() (3) with monodentate azide coordination. The ligation of dipropylenetriamine (dpt) gives a end-on (mu-1,1) diazido-bridged binuclear copper complex [Cu(dpt)(mu-N(3))](2)(ClO(4))(2) (4). The crystal and molecular structures of these complexes have been solved. Variable-temperature EPR results of 1 and 2 are identical and indicate the presence of both ferromagnetic and antiferromagnetic interactions within the dimer, the former dominating at low temperatures and the latter at high temperatures. The unusual temperature-dependent magnetic moment and EPR spectra of this dimer reveal the presence of temperature-dependent population of two triplet states, one being caused by antiferromagnetic and the other by ferromagnetic interaction, the former transforming to the latter on cooling. While the interaction of ground spin doublets of the two metal centers gives rise to a ferromagnetic coupling of J(g) = 90.73 cm(-1), the other coupling of J(e) = -185.64 cm(-1) is suggested to be caused by the interaction between an electron in one metal center and an electron from the azide of the other monomer by excitation of a d-electron to the empty ligand orbital. The ferromagnetic state is energetically favored by 104.39 cm(-1). Compound 3 exhibits axial spectra at room temperature and 77 K, and variable-temperature magnetic susceptibility data indicate that the copper centers form a weakly antiferromagnetic one-dimensional chain with J = -0.11 cm(-1). In the case of 4, the unique presence of two nonidentical dimeric units with different bond lengths and bond angles within the unit cell as inferred by crystal structure is proved by single-crystal EPR spectroscopy.     

A Facile Synthesis of 7,8-DI Aryl Coumarino and Flavano Benzo-Thiophenes

The key step for the synthesis of 7-hydroxy 2,3-diarylsubstituted benzothiophenes 5a-f , by starting from substituted 2-aryl-2-((2-methoxy phenyl)thio)acetophenones 3a-f as an intermediate, consists of a Friedel-Crafts cyclization followed by demethylation by Lewis acids like BF 3 OEt 2 and AlCl 3 in DCM.     

Forced responses of solid axially polarized piezoelectric ceramic finite cylinders with internal losses

A method is presented to determine the forced responses of piezoelectric cylinders using weighted sums of only certain exact solutions to the equations of motion and the Gauss electrostatic conditions. One infinite set of solutions is chosen such that each field variable is expressed in terms of Bessel functions that form a complete set in the radial direction. Another infinite set of solutions is chosen such that each field variable is expressed in terms of trigonometric functions that form a complete set in the axial direction. Another solution is used to account for the electric field that can exist even when there is no vibration. The weights are determined by using the orthogonal properties of the functions and are used to satisfy specified, arbitrary, axisymmetric boundary conditions on all the surfaces. Special cases including simultaneous mechanical and electrical excitation of cylinders are presented. All numerical results are in excellent agreement with those obtained using the finite element software ATILA. For example, the five lowest frequencies at which the conductance and susceptance of a stress-free cylinder, of length 10 mm and radius 5 mm, reach a local maximum or minimum differ by less than 0.01% from those computed using ATILA.     

Parametric identification of nonlinear systems using multiple trials

It is observed that the harmonic balance (HB) method of parametric identification of nonlinear system may not give right identification results for a single test data. A multiple-trial HB scheme is suggested to obtain improved results in the identification, compared with a single sample test. Several independent tests are conducted by subjecting the system to a range of harmonic excitations. The individual data sets are combined to obtain the matrix for inversion. This leads to the mean square error minimization of the entire set of periodic orbits. It is shown that the combination of independent test data gives correct results even in the case where the individual data sets give wrong results.     

Free radical 5-exo-dig cyclization as the key step in the synthesis of bis-butyrolactone natural products: experimental and theoretical studies

Radical cyclization reactions were performed by 5-exo-dig mode to yield cis-fused bicyclic systems, leading to the synthesis of bis-butyrolactone class of natural products. The study was aimed at understanding the impact of alkyl side chains of furanoside ring systems in L-ara configuration on the radical cyclization. It was amply demonstrated by experimental studies that the increase in the length of the alkyl side chain has an effect on the cyclization: while efficient cyclization reactions could be realized with methyl and ethyl side chains, the yields were significantly reduced in the case of n-pentyl side chain. Theoretical studies using DFT and (RO)MP2 methods were carried out to analyze the influence of the substitution pattern on the cyclization barriers.     

Search for new red phosphors using genetic algorithm-assisted combinatorial chemistry

A genetic algorithm was employed in association with high-throughput synthesis and characterization in an attempt to search for red phosphors with high photoluminescent intensity. A tetravalent manganese-doped alkali earth germanium oxide system, with an emission color close to a desirable deep red, was screened with the assistance of a genetic algorithm to pinpoint the phosphor exhibiting the highest photoluminescence. As the genetic algorithm was in progress, the PL intensity increased and maximized in the fourth generation. The highest and the average PL intensity of the fourth generation improved by 23 and 120%, respectively, compared with that of the first generation.     

Reporting of quantitative oxygen mapping in EPR imaging

Oxygen maps derived from electron paramagnetic resonance spectral-spatial imaging (EPRI) are based upon the relaxivity of molecular oxygen with paramagnetic spin probes. This technique can be combined with MRI to facilitate mapping of pO(2) values in specific anatomic locations with high precision. The co-registration procedure, which matches the physical and digital dimensions of EPR and MR images, may present the pO(2) map at the higher MRI resolution, exaggerating the spatial resolution of oxygen, making it difficult to precisely distinguish hypoxic regions from normoxic regions. The latter distinction is critical in monitoring the treatment of cancer by radiation and chemotherapy, since it is well-established that hypoxic regions are three or four times more resistant to treatment compared to normoxic regions. The aim of this article is to describe pO(2) maps based on the intrinsic resolution of EPRI. A spectral parameter that affects the intrinsic spatial resolution of EPRI is the full width at half maximum (FWHM) height of the gradient-free EPR absorption line in frequency-encoded imaging. In single point imaging too, the transverse relaxation times (T(2)(?)) limit the resolution since the signal decays by exp(-t(p)/T(2)(?)) where the delay time after excitation pulse, t(p), is related to the resolution. Although the spin densities of two point objects may be resolved at this separation, it is inadequate to evaluate quantitative changes of pO(2) levels since the linewidths are proportionately affected by pO(2). A spatial separation of at least twice this resolution is necessary to correctly identify a change in pO(2) level. In addition, the pO(2) values are blurred by uncertainties arising from spectral dimensions. Blurring due to noise and low resolution modulates the pO(2) levels at the boundaries of hypoxic and normoxic regions resulting in higher apparent pO(2) levels in hypoxic regions. Therefore, specification of intrinsic resolution and pO(2) uncertainties are necessary to interpret digitally processed pO(2) illustrations.     

Synthesis and antimicrobial activity of 6,6′‐arylidene‐bis‐[5‐hydroxy‐9‐methyl‐2,3‐diaryl thieno[3,2‐g‐]thiocoumarins]

A variety of novel 6,6′‐arylidene‐bis‐[5‐hydroxy‐9‐methyl‐2,3‐diaryl‐thieno[3,2‐g]thiocoumarins] 3a‐d , 4a‐d , 5a‐d , and 6a‐d were obtained by a reaction between 5‐hydroxy‐9‐methyl‐2,3‐diarylthieno[3,2‐g]thiocoumarins 1a‐d with aromatic aldehydes 2a‐d in isopropyl alcohol. The synthesized compounds were tested for their antimicrobial activity.     

An efficient one-pot three-component synthesis of imidazol-2-ones using [Bmim]BF4 ionic liquid

A mild and efficient method was developed for preparation of imidazol-2-ones via one-pot three-component condensation of 1,3-cyclic diketones, aryl glyoxals and urea using [Bmim]BF₄ ionic liquid. Excellent yields, short reaction time, simple work-up, and reusability of IL are advantages of this procedure.     

Investigation on electromechanical properties of A-site donor rare-earth modified tetragonal (4 mm) lead barium niobate (PBN55) ceramics

In this paper, Pb_0.55?(3y/2)Ce_yBa_0.45Nb₂O₆ ceramics with tetragonal tungsten–bronze structure prepared through the solid-state reaction method and characterized for phase formation, density, dielectric and piezoelectric properties are reported. The XRD analysis showed the presence of a tetragonal tungsten–bronze structure, which intensified with increasing Ce content. The stability of the tetragonal tungsten–bronze phase has been discussed with the electronegativity difference and the tolerance factor. The Curie temperature (T_c) systematically lowered when Ce was incorporated into tetragonal PBN lattice. The room-temperature dielectric constant (ε_RT) of Ce-modified lead barium niobate (PBN) compositions has enhanced from C₀ to C₃ and thereafter decreased. The influence of Ce on piezoelectric properties of tetragonal PBN system has been evaluated. The piezoelectric coefficients (d, g, k and Q_m) were characterized. The C₃ composition exhibited optimum piezoelectric properties in the series, and this composition could be suitable for piezoelectric applications.