Multi-State Second-Order Nonlinear Optical Switches Incorporating One to Three Benzazolo-Oxazolidine Units: A Quantum Chemistry Investigation

This contribution employs quantum chemistry methods to describe the variations of the second nonlinear optical responses of molecular switches based on benzazolo-oxazolidine (BOX) units, connected by π-linkers, along their successive opening/closing. Under the fully closed forms, all of them display negligible first hyperpolarizability (β) values. When one BOX is opened, which is sketched as C→O, a push–pull π-conjugated segment is formed, having the potential to enhance β and to set the depolarization ratio (DR) to its one-dimensional-like value (DR = 5). This is observed when only one BOX is open, either for the monoBOX species (C→O) or for the diBOX (CC→CO) and triBOX (CCC→CCO) compounds, i.e., when the remaining BOXs stay closed. The next BOX openings have much different effects. For the diBOXs, the second opening (CO→OO) is associated with a decrease of β, and this decrease is tuned by controlling the conformation of the π-linker, i.e., the centrosymmetry of the whole compound because β vanishes in centrosymmetric compounds. For the triBOXs, the second opening gives rise to a Λ-shape compound, with a negligible change of β, but a decrease of the DR whereas, along the third opening, β remains similar and the DR decreases to the typical value of octupolar systems (DR = 1.5).     

Access to nonisocyanate poly(thio)urethanes: A comparative study

This article describes the synthesis of new cyclic compounds able to react with amines to get nonisocyanate polyurethanes (NIPUs). The contribution of the most studied five‐membered cyclic carbonate was compared to five‐membered cyclic dithiocarbonate analogous and to a six‐membered cyclic carbonate. Difunctional reactive species were obtained by a simple substitution reaction or an efficient thiol–ene coupling reaction. The products, obtained with high yields, were characterized by 1H NMR, 13C NMR, and Fourier tansform infrared spectroscopy analysis. The dicyclocarbonates were then used to synthesize NIPUs by step growth polymerization with several diamines. These materials exhibited glass transition temperatures from 19 to ?29 °C, molar mass from 1800 to 20,400 g mol^?1, and a 20% mass loss temperature (T_d = 20%) between 249 and 296 °C. Such materials are interesting candidates for coating applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3284–3296     

Regiospecific synthesis of cepanolide,a cancer chemoprotective micronutrient found in green onions

The naturally occurring γ-hydroxy-β-sulfanylbutenolide cepanolide and a range of new analogues were synthesized in concise, regiospecific manner through the combined use of 2-silyloxyfuran oxyfunctionalization and tandem thio-Michael addition/elimination.     

An eigenvector‐based linear reconstruction approach for time stepping in discontinuous Galerkin scheme used to solve shallow water equations

Discontinuous Galerkin (DG) methods have shown promising results for solving the two‐dimensional shallow water equations. In this paper, the classical Runge–Kutta (RK) time discretisation is replaced by the eigenvector‐based reconstruction (EVR) that allows the second‐order time accuracy to be achieved within a single time‐stepping procedure. Moreover, the EVRDG approach yields stable solutions near drying and wetting fronts, whereas the classical RKDG approach yields instabilities. The proposed EVRDG technique is compared with the original RKDG approach on various test cases with analytical solutions. The EVRDG solutions are shown to be as accurate as those obtained with the RKDG scheme. Besides, the EVRDG scheme is 1.6 times faster than the RKDG method. Simulating dambreaks involving dry beds confirms that EVRDG scheme gives correct solutions, whereas the RKDG method yields instabilities. Copyright © 2012 John Wiley & Sons, Ltd.     

Lanthanide Identity Governs Guest-Induced Dimerization in LnIII[15-MC N(L-pheHA)-5])3+ Metallacrowns

Series of lanthanide-containing metallic coordination complexes are frequently presented as structurally analogous, due to the similar chemical and coordinative properties of the lanthanides. In the case of chiral (Ln^III[15-MC _N(L-pheHA)-5])³⁺ metallacrowns (MCs), which are well established supramolecular hosts, the formation of dimers templated by a dicarboxylate guest (muconate) in solution of neutral pH is herein shown to have a unique dependence on the identity of the MC's central lanthanide. Calorimetric data and nuclear magnetic resonance diffusion studies demonstrate that MCs containing larger or smaller lanthanides as the central metal only form monomeric host-guest complexes whereas analogues with intermediate lanthanides (for example, Eu, Gd, Dy) participate in formation of dimeric host-guest-host compartments. The driving force for the dimerization event across the series is thought to be a competition between formation of highly stable MCs (larger lanthanides) and optimally linked bridging guests (smaller lanthanides).     

Derivation of Lanthanide Series Crystal Field Parameters From First Principles

Two series of lanthanide complexes have been chosen to analyze trends in the magnetic properties and crystal field parameters (CFPs) along the two series: The highly symmetric LnZn₁₆(picHA)₁₆ series (Ln=Tb, Dy, Ho, Er, Yb; picHA=picolinohydroxamic acid) and the [Ln(dpa)₃](C₃H₅N₂)₃ ⋅ 3H₂O series (Ln=Ce–Yb; dpa=2,6-dipicolinic acid) with approximate three-fold symmetry. The first series presents a compressed coordination sphere of eight oxygen atoms whereas in the second series, the coordination sphere consists of an elongated coordination sphere formed of six oxygen atoms. The CFPs have been deduced from ab initio calculations using two methods: The AILFT (ab initio ligand field theory) method, in which the parameters are determined at the orbital level, and the ITO (irreducible tensor operator) decomposition, in which the problems are treated at the many-electron level. It has been found that the CFPs are transferable from one derivative to another, within a given series, as a first approximation. The sign of the second-order parameter differs in the two series, reflecting the different environments. It has been found that the use of the strength parameter S allows for an easy comparison between complexes. Furthermore, in both series, the parameters have been found to decrease in magnitude along the series, and this decrease is attributed to covalent effects.     

An Improved Procedure for the Synthesis of Prostaglandin Analogues

Hydrozirconation-iodination of a terminal acetylene followed by lithium-iodide exchange and finally dilithio cyanocuprate mediated conjugate addition to an appropriate cyclopentenone is reported as an efficient method for the synthesis of prostaglandin analogues.     

Simulations of ferrite-dielectric-wire composite negative index materials

We perform extensive finite difference time domain simulations of ferrite based negative index of refraction composites. A wire grid is employed to provide negative permittivity. The ferrite and wire grid interact to provide both negative and positive index of refraction transmission peaks in the vicinity of the ferrite resonance. Notwithstanding the extreme anisotropy in the index of refraction of the composite, negative refraction is seen at the composite air interface allowing the construction of a focusing concave lens with a magnetically tunable focal length.