Honeycomb nets with interpenetrating frameworks involving iminodiacetato-copper(II) blocks and bipyridine spacers: syntheses, characterization, and magnetic studies

Three coordination polymers of copper(II), viz. ([Cu(ida)(4,4'-bipyH)]ClO(4))( proportional, variant ) (1), ([Cu(2)(ida)(2)(micro-4,4'-bipy)].2H(2)O)( proportional, variant ) (2), and [Cu(2)(ida)(2)(bpa)]( proportional, variant ) (3) have been synthesized by the process of self-assembly using Cu(ida) [ida = iminodiacetate(2-)] as the building block and 4,4'-bipyridyl and 1,2-bis(4-pyridyl)ethane (bpa) as linkers. Crystals of 1 are orthorhombic, of space group Pna2(1), with a = 13.8956(12) A, b = 16.3362(16) A, c = 7.3340(12), and Z = 4. Both compounds 2 and 3 crystallize in monoclinic space group P2(1)/a with a = 10.1887(8) A (9.6779(10) A for 3), b = 8.0008(11) A (9.1718(10) A), c = 11.6684(9) A (12.9144(12) A), beta = 98.307(11) degrees (102.796(18) degrees ), and Z = 2 (2). Compound 1 has a zigzag chain structure with an extensive hydrogen-bonded network while compounds 2 and 3 are honeycomb (6,3) nets with interpenetrating structures. Variable temperature (2-300 K) magnetic study indicates the presence of weak antiferromagnetic interactions (J = 0.82 +/- 0.01 cm(-)(1)) in 1 and ferromagnetic in 2 (J = -0.45 +/- 0.05 cm(-)(1)) and 3 (J = -0.21 +/- 0.02 cm(-)(1)). The extent of planarity of the bridging "Cu-O-C-O-Cu" moiety, acting as the super-exchange pathway between the neighboring copper centers, probably controls the sign of the magnetic exchange coupling in these compounds.     

Structure and spectroscopic aspects of water‐halide ion clusters: A study based on a conjunction of stochastic and quantum chemical methods

In this article, we propose a stochastic search based method, namely genetic algorithm in conjunction with density functional theory to evaluate structures of water‐halide microclusters, with the halide ion being Cl^?, Br^?, and I^?. Once the structures are established, we evaluate the infrared spectroscopic modes, vertical detachment energies and natural population analysis based charges. We compare our results with available experimental and theoretical results. © 2012 Wiley Periodicals, Inc.     

Oxovanadium(IV) and -(V) complexes of dithiocarbazate-based tridentate Schiff base ligands: syntheses,structure, and photochemical reactivity of compounds involving imidazole derivatives as coligands

The tridentate dithiocarbazate-based Schiff base ligands H(2)L (S-methyl-3-((5-R-2-hydroxyphenyl)methyl)dithiocarbazate, R = NO(2), L = L(2); R = Br, L = L(3)) react with [VO(acac)(2)] in the presence of imidazole derivatives as coligands to form oxovanadium(IV) and cis-dioxovanadium(V) complexes. With benzimidazole and N-methylimidazole, the products are oxovanadium(IV) complexes, viz. [VOL(3)(BzIm)].0.5CH(3)CN (1a) and [VOL(N-MeIm)(2)] (L = L(3), 1b; L = L(2), 1c), respectively. In both 1a,b, the O and S donor atoms of the tridentate ligand are cis to the terminal oxo group (in the "equatorial" plane) and mutually trans, but the N donor atom is respectively cis and trans to the oxo atom, as revealed from X-ray crystallography. When imidazole or 4-methylimidazole is used as the ancillary ligand, the products obtained are water-soluble cis-dioxovanadium(V) complexes [VO(2)L(R'-ImH)] (L = L(3) and L(2), R' = H and Me, 2a-d). These compounds have zigzag chain structures in the solid state as confirmed by X-ray crystallographic investigations of 2a,d, involving an alternating array of LVO(2)(-) species and the imidazolium counterions held together by Coulombic interactions and strong hydrogen bonding. Complexes 2a-d are stable in water or methanol. In aprotic solvents, viz. CH(3)CN, DMF, or DMSO, however, they undergo photochemical transformation when exposed to visible light. The putative product is a mixed-oxidation divanadium(IV/V) species obtained by photoinduced reduction as established by EPR, electronic spectroscopy, and dynamic (1)H NMR experiments.     

Monopolar surfaces

Following the development of a methodology for determining the apolar components as well as the electron donor and the electron acceptor parameters of the surface tension of polar surfaces, surfaces of a number of quite common materials were found to manifest virtually only electron donor properties and no, or hardly, any electron acceptor properties. Such materials may be called monopolar; they can strongly interact with bipolar materials (e.g., with polar liquids such as water); but one single polar parameter of a monopolar material cannot contribute to its energy of cohesion. Monopolar materials manifesting only electron acceptor properties also may exist, but they do not appear to occur in as great an abundance. Among the electron donor monopolar materials are: polymethylmethacrylate, polyvinylalcohol, polyethyleneglycol, proteins, many polysaccharides, phospholipids, nonionic surfactants, cellulose esters, etc. Strongly monopolar materials of the same sign repel each other when immersed or dissolved in water or other polar liquids. The interfacial tension between strongly monopolar surfaces and water has a negative value. This leads to a tendency for water to penetrate between facing surfaces of a monopolar substance and hence, to repulsion between the molecules or particles of such a monopolar material, when immersed in water, and thus to pronounced solubility or dispersibility. Monopolar repulsion energies can far outweigh Lifshitz-van der Waals attractions as well as electrostatic and "steric" repulsions. In aqueous systems the commonly observed stabilization effects, which usually are ascribed to "steric" stabilization, may in many instances be attributed to monopolar repulsion between nonionic stabilizing molecules. The repulsion between monopolar molecules of the same sign can also lead to phase separation in aqueous solutions (or suspensions), where not only two, but multiple phases are possible. Negative interfacial tensions between monopolar surfactants and the brine phase can be the driving force for the formation of microemulsions; such negative interfacial tensions ultimately decay and stabilize at a value very close to zero. Strongly monopolar macromolecules or particles surrounded by oriented water molecules of hydration can still repel each other, albeit to an attenuated degree. This repulsion was earlier perceived as caused by "hydration pressure". A few of the relevant colloid and surface phenomena are reviewed and re-examined in the light of the influence of surface monopolarity on these phenomena.     

Coupling Effects of Electrostatic Interactions and Salt Concentration Gradient in Polymer Translocation through a Nanopore: A Coarse-Grained Molecular Dynamics Simulations Study

We study the influence of polymer pore interactions and focus on the role played by the concentration gradient of salt in the translocation of polyelectrolytes (PE) through nanopores explicitly using coarse-grained Langevin dynamics simulations. The mean translocation time is calculated by varying the applied voltage, the pH, and the salt concentration gradient. Changing the pH can alter the electrostatic interaction between the protein pore and the polyelectrolyte chain. The polymer pore interaction is weakened by the increase in the strength of the externally applied electric field that drives translocation. Additionally, the screening effect of the salt can reduce the strong charge-charge repulsion between the PE beads which can make translocation faster. The simulation results show there can be antagonistic or synergistic coupling between the salt concentration-induced screening effect and the drift force originating from the salt concentration gradient thereby affecting the translocation time. Our simulation results are explained qualitatively with free energy calculations.     

Simulated annealing‐based optimal control over tunneling process through SDWP and Eckart barrier: A momentum basis representation

For a reaction to proceed via tunneling mechanism, it is essential that the reactants will cross the potential barrier (E_P), where its initial energy (E₀) is below the potential barrier E_P. Tunneling probability τ is defined as the probability of having momentum higher than k_m, where . In the momentum basis representation, τ can be directly calculated by integrating from the limit k_m to infinity, where is the wave function in the momentum space. Instead of the continuous basis, if we chose momentum grid space, τ can be expressed as . Our target here is to increase this τ by applying a polychromatic field, so that the reaction rate can be enhanced. By applying Simulated Annealing technique we have designed some polychromatic electric fields, spatially symmetric and asymmetric type, which enhances the tunneling rate in symmetric double well system and Eckart barrier confined in an infinite well.     

Synthesis and reactivity of tricarbonyl(1-methoxycarbonyl-5-phenylpentadienyl)iron(1+) cation

Tricarbonyl(1-methoxycarbonyl-5-phenylpentadienyl)iron(1+) hexafluorophosphate (7) was prepared in two steps from tricarbonyl(methyl 6-oxo-2,4-hexadienoate)iron. While addition of carbon and heteroatom nucleophiles to 7 generally occurs at the phenyl-substituted dienyl carbon to afford (2,4-dienoate)iron products, the addition of phthalimide proceeded at C2 to afford a (pentenediyl)iron product (18). Complex 18 was structurally characterized by X-ray diffraction analysis.     

Cosmologies with Variable G and Λ from Action Principle

Cosmologies with variable G and are developed in this paper from an action principle, and some exact cosmological models are presented. These models indicate that the era of variable G and must have occurred, if at all, prior to other possible eras like radiation and dust.     

Meniscus instability in a thin elastic film

A new kind of meniscus instability leading to the formation of stationary fingers with a well-defined spacing has been observed in experiments with elastomeric films confined between a plane rigid glass and a thin curved glass plate. The wavelength of the instability increases linearly with the thickness of the confined film, but it is remarkably insensitive to the compliance and the energetics of the system. However, lateral amplitude (length) of the fingers depends on the compliance of the system and on the radius of curvature of the glass plate. A simple linear stability analysis is used to explain the underlying physics and the key observed features of the instability.     

Failure of elastomeric polymers due to rate dependent bond rupture

A new cohesive zone model is developed in order to study the mechanisms of adhesive and cohesive failures of soft rubbery materials. The fracture energy is estimated here using a strategy similar to that of Lake and Thomas (LT) by considering the dissipation of stored elastic energy followed by the extension and relaxation of polymer chains. The current model, however, departs from that of LT in that the force needed to break an interfacial bond does not have a fixed value; instead, it depends on the thermal state of the system and the rate at which the force is transmitted to the bond. While the force required to rupture a chain is set by the rules of thermomechanically activated bond dissociation kinetics, extension of a polymer chain is modeled within both the linear and nonlinear models of chain elasticity. Closed form asymptotic solutions are obtained for the dependence of crack propagation speed on the energy release rate, which are valid in two regimes: (I) slow crack velocity or short relaxation time for bond dissociation; (II) fast crack velocity or long relaxation time for bond dissociation. The rate independent and the zero temperature limit of this theory correctly reduces to the fracture model of LT. Detailed comparisons are made with a previous work by Chaudhury et al. which carried out an approximate analysis of the same problem.