Delicate crystal structure changes govern the magnetic properties of 1D coordination polymers based on 3d metal carboxylates

Homo- and heterometallic 1D coordination polymers of transition metals (Co II, Mn II, Zn II) have been synthesized by an in-situ ligand generation route. Carboxylato-based complexes [Co(PhCOO)2]n (1 a, 1 b), [Co(p-MePhCOO)2]n (2), [ZnMn(PhCOO)4]n (3), and [CoZn(PhCOO)4]n (4) (PhCOOH=benzoic acid, p-MePhCOOH=p-methylbenzoic acid) have been characterized by chemical analysis, single-crystal X-ray diffraction, and magnetization measurements. The new complexes 2 and 3 crystallize in orthorhombic space groups Pnab and Pcab respectively. Their crystal structures consist of zigzag chains, with alternating M(II) centers in octahedral and tetrahedral positions, which are similar to those of 1 a and 1 b. Compound 4 crystallizes in monoclinic space group P2 1/c and comprises zigzag chains of M II ions in a tetrahedral coordination environment. Magnetic investigations reveal the existence of antiferromagnetic interactions between magnetic centers in the heterometallic complexes 3 and 4, while ferromagnetic interactions operate in homometallic compounds (1 a, 1 b, and 2). Compound 1 b orders ferromagnetically at TC=3.7 K whereas 1 a does not show any magnetic ordering down to 330 mK and displays typical single-chain magnet (SCM) behavior with slowing down of magnetization relaxation below 0.6 K. Single-crystal measurements reveal that the system is easily magnetized in the chain direction for 1 a whereas the chain direction coincides with the hard magnetic axis in 1 b. Despite important similarities, small differences in the molecular and crystal structures of these two compounds lead to this dramatic change in properties.     

Development and validation of high-performance liquid chromatography method for determination of clarithromycin in pharmaceutical tablets

Clarithromycin is a very important macrolide antibiotic used to treat bacterial infections in human and veterinary medicine. This study reports the development and validation of cost-effective, simple, precise, accurate, and robust high-performance liquid chromatography (HPLC) for the determination of clarithromycin (CLA) in tablets. Reversed-phase chromatography was conducted using a standard column at 55°C with ultraviolet detection at 215 nm. A mobile phase consisting of acetonitrile –2-methyl-2-propanol –potassium phosphate buffer was used at a flow rate of 1.0 mL/min. The proposed method displayed good linearity, precision, accuracy, robustness, and specificity. The present HPLC was compared with capillary electrophoresis and bioassay methods and the results indicated that there was no significant difference between these methods. Moreover, the obtained results demonstrated the validity of the isocratic HPLC, which allows reliable quantitation of CLA in pharmaceutical samples. Thus, it can be used as a substitute alternative methodology for the routine quality control of this medicine, in situations where other methods are less accessible in the laboratory.     

GRASP-based heuristic algorithm for the multi-product multi-vehicle inventory routing problem

In this paper, we introduce an improved Greedy Randomized Adaptive Search Procedure (GRASP) based heuristic for the multi-product multi-vehicle inventory routing problem (MMIRP). The inventory routing problem, which combines the vehicle-routing problem and the inventory control decisions, is one of the most important problems in combinatorial optimization field. To deal with the MMIRP, we develop a GRASP-based heuristic (GBH). Each GBH iteration consists of two sequential phases; the first phase is a Greedy Randomized Procedure, in which, the best tradeoff between the inventory holding cost and routing cost is looked. Then, in the second phase, as local search for the GRASP, we use the Tabu search (TS) meta-heuristic to improve the solution found in the first phase. The GBH two phases are repeated until some stopped criterion is met. Our proposed method is evaluated on two benchmark data sets, and successfully compared with two state-of-the-art algorithms.     

Existence and stability results for semilinear systems of impulsive stochastic differential equations with fractional Brownian motion

Some results on the existence and uniqueness of mild solution for a system of semilinear impulsive differential equations with infinite fractional Brownian motions are proved. The approach is based on Perov's fixed point theorem and a new version of Schaefer's fixed point theorem in generalized Banach spaces. The relationship between mild and weak solutions and the exponential stability of mild solutions are investigated as well. The abstract theory is illustrated with an example.     

Evidence of the central tetrathiafulvalene bond opening by copper(II) salts. In situ generation of 2,3-bis(2′-cyanoethylchalcogeno)-7,8-benzo-1,4,6,9-tetrathia-10-ceto spiro[4,5]decane

The two-electrons oxidation of 4,5-benzo-6,7-bis(2′-cyanoethylthio) TTF (CETBz-TTF) and 4,5-benzo-6,7-bis(2′-cyanoethylseleno) TTF (CESBz-TTF) with Cu²⁺X₂ (X = Cl⁻, ) leads to the formation of 2,3-bis(2′-cyanoethylchalcogeno)-7,8-benzo-1,4,6,9-tetrathia-10-ceto spiro[4,5]decane after opening of the -C-S- bond of the central TTF core.     

Optoelectronic properties of SnO_2 thin films sprayed at different deposition times

This article presents the elaboration of tin oxide(SnO_2) thin films on glass substrates by using a home-made spray pyrolysis system. Effects of film thickness on the structural, optical, and electrical film properties are investigated. The films are characterized by several techniques such as x-ray diffraction(XRD), atomic force microscopy(AFM), ultravioletvisible(UV–Vis) transmission, and four-probe point measurements, and the results suggest that the prepared films are uniform and well adherent to the substrates. X-ray diffraction(XRD) patterns show that SnO_2 film is of polycrystal with cassiterite tetragonal crystal structure and a preferential orientation along the(110) plane. The calculated grain sizes are in a range from 32.93 nm to 56.88 nm. Optical transmittance spectra of the films show that their high transparency average transmittances are greater than 65% in the visible region. The optical gaps of SnO_2 thin films are found to be in a range of 3.64 e V–3.94 e V. Figures of merit for SnO_2 thin films reveal that their maximum value is about 1.15 × 10-4-1?atλ = 550 nm. Moreover, the measured electrical resistivity at room temperature is on the order of 10-2?·cm.     

2D porous honeycomb polymers versus discrete nanocubes from trigonal trinuclear complexes and ligands with variable topology

Trinuclear building block {Fe(2)NiO(Piv)(6)} (Piv = pivalate), which possessed pseudo-D(3h) symmetry, was linked by two ligands, pseudo-D(3h) ligand tris-(4-pyridyl)pyridine (L1) and C(2v) ligand 4-(N,N-dimethylamino)phenyl-2,6-bis(4-pyridyl)pyridine (L2) into two products with different topologies: 2D coordination polymer [Fe(2)NiO(Piv)(6)(L1)](n) (1), and discrete molecule [{Fe(2)NiO(Piv)(6)}(8) {L2}(12)], which had a nanocube structure (2). In compound 1, trinuclear {Fe(2)NiO(Piv)(6)} blocks were linked through ligand L1 into layers with honeycomb topology. In compound 2, eight trinuclear blocks were located in the vertices of the nanocube, with each L2 ligand linked to two {Fe(2)NiO(Piv)(6)} units. In the crystal structure, these nanocubes formed infinite catenated chains. Analysis of possible structures that could be assembled from these building blocks showed that compounds 1 and 2 corresponded to their respective predicted topologies. Compound [1?solvent] possessed a porous structure, in which the voids were filled by solvent molecules (DMF or DMSO). This structure was retained following desolvation, and compound 1 absorbed significant quantities of N(2) and H(2) at 78?K (S(BET) = 730?m(2) g(-1), H(2) sorption capacity: 0.9?% by weight at 865?Torr). Desolvation of [2?solvent] led to disorder of its crystal structure, and compound 2 only adsorbed negligible quantities of N(2) but adsorbed 0.27?% H(2) (by weight) at 855?Torr and 78?K. The magnetic properties of these complexes (temperature dependence of molar magnetic susceptibility) were governed by the magnetic properties of the trinuclear "building block".     

The role of the bridging group in exchange coupling in dinuclear homo- and heterometallic Ni(ii) and Co(ii) complexes with oxalate, oxamidate and dithiooxamidate bridges

Six homodinuclear and two heteronuclear complexes Tp(Np)Co-C(2)O(4)-CoTp(Np) (1), Tp(Np)Co-C(2)O(4)-NiTp(Cy) (2), Tp(Cy)Ni-C(2)O(4)-NiTp(Cy) (3), Tp(Np)Co-C(2)O(2)(NH)(2)-CoTp(Np) (4), Tp(Cy)Ni-C(2)O(2)(NH)(2)-NiTp(Cy) (5), Tp(Np)Co-C(2)S(2)(NH)(2)-CoTp(Np) (6), Tp(Np)Co-C(2)S(2)(NH)(2)-NiTp(Cy) (7), Tp(Cy)Ni-C(2)S(2)(NH)(2)-NiTp(Cy) (8) (Tp(Np) = tris(3-neopentylpyrazolyl)borate, Tp(Cy) = tris(3-cyclohexylpyrazolyl)borate), were synthesized and characterized by mass spectrometry, electronic spectroscopy and X-ray crystallography. These compounds possess similar molecular structures, with the metal ions linked by bridging oxalate (1-3), oxamidate (4 and 5) or dithiooxamidate (6-8) ions. The heteronuclear nature of compounds 2 and 7 was additionally confirmed by high-resolution mass spectrometry. The magnetic properties of the Co(2+) complexes were modelled taking into account zero-field splitting of this ion, yielding D-values for Co(2+) in the range -17(1) to -50(1) cm(-1). All the metal ion pairs in compounds 1-8 are antiferromagnetically-coupled, with J values between -10.0(1) and -45.0(2) cm(-1) (via the exchange Hamiltonian ?(ex.) = -2J?(1)?(2)) and |J| increasing in the order oxalate < oxamidate < dithiooxamidate. This tendency can be attributed to greater M-S bond covalency compared to M-N or M-O bonds (M = Co(2+) and Ni(2+)). It was found that this antiferromagnetic coupling of Co(2+) and Ni(2+) ions through oxalate is more efficient for these tris(pyrazolyl)borate complexes than for similar oxalate-bridged systems with neutral aliphatic amine ligands.