Regioselective remote CH fluoroalkylselenolation of 8-aminoquinolines

Herein, the direct C-5 fluoroalkylselenolation of 8-aminoquinolines is described. The Pd-catalyzed reaction is performed with the in situ generated fluoroalkylselenyl chloride and various 8-aminoquinoline amides or sulfonamides. The desired products were formed in moderate to excellent yields.     

Can Coordination‐Driven Supramolecular Self‐Assembly Reactions Be Conducted from Fully Aliphatic Linkers?

The reaction between a preassembled Cu^I bimetallic molecular clip with a short intermetallic distance and a series of fully aliphatic cyano‐capped ditopic linkers with increasing lengths was investigated. It is shown that, depending on the length of the ditopic linkers, the rational design of unprecedented supramolecular compact metallacycles containing fully aliphatic walls is possible. The specific preorganized molecular arrangement of the molecular clip used favors stabilizing interlinker London dispersion interactions, which allow, as the length of the linkers increases, the selective formation of discrete compact metallacycles at the expense of 1D coordination polymers. The generalizability of this approach was demonstrated by the reaction of fully aliphatic cyano‐capped linkers with two other types of preassembled Cu^I bimetallic molecular clips that also had short intermetallic distances.     

Supramolecular assemblies based on organometallic quinonoid linkers: a new class of coordination networks

Self-assembly of coordination frameworks exhibiting original architectures is an active area of research. Generally, such assemblies are constructed from organic spacers and transition metals of different geometrical structures. Herein, we report a novel class of supramolecular coordination assemblies with organometallic linkers based on metalated quinonoid and thioquinonoid complexes that serve as spacers. The organometallic ligands are stable and have the general formula [Cp*M(eta(4)-benzoquinone)] (o- and p-benzoquinone, Cp*=C(5)Me(5), M=Rh, Ir) and [Cp*Ir(eta(4)-thiobenzoquinone)] (o- and p-thiobenzoquinone). These units bind through both oxygen or sulfur atoms to metal ions of different coordination geometry, such as Cu(I), Ag(I), and Pt(II), to generate supramolecular coordination networks, with the metalated quinonoid or thioquinonoid linkers acting as backbones and the metal centers as nodes. This novel family of supramolecular assemblies exhibits short pi-pi and MM interactions. These results illustrate successfully the role of the organometallic linkers to produce an impressive range of novel supramolecular architectures that hold promise for the development of functional materials.     

Some variants of the classical Aubin–Lions Lemma

This paper explores two generalizations of the classical Aubin–Lions Lemma. First, we give a sufficient condition to commute weak limit and multiplication of two functions. We deduce from this criteria a compactness theorem for degenerate parabolic equations. Second, we state and prove a compactness theorem for noncylindrical domains, including the case of dual estimates involving only divergence-free test functions.     

Heteroepitaxial growth of thin InAs layers on GaAs(1 0 0) misoriented substrates: A structural and morphological comparison

Thin InAs epilayers were grown on GaAs(1 0 0) substrates exactly oriented and misoriented toward [1 1 1]A direction by atmospheric pressure metalorganic vapor phase epitaxy. InAs growth was monitored by in situ spectral reflectivity. Structural quality of InAs layers were studied by using high-resolution X-ray diffraction. No crystallographic tilting of the layers with respect to any kind of these substrates was found for all thicknesses. This result is discussed in terms of In-rich growth environment. InAs layers grown on 2° misoriented substrate provide an improved crystalline quality. Surface roughness of InAs layers depend on layer thickness and substrate misorientation.     

Usefulness of cyclodextrin media for the determination of α-cypermethrin by photochemically induced fluorescence: analytical applications to natural waters

The photochemically induced fluorescence (PIF) spectral properties of α-cypermethrin in organic solvents (hexane, dichloromethane, acetonitrile, ethanol) and in cyclodextrin aqueous solutions (β-CD and 2-hydroxypropyl-β-CD, 2-HP-β-CD) were investigated. The photolysis kinetics of α-cypermethrin were evaluated in the various media. The PIF signal was found to be significantly enhanced in the CD media relative to the organic solvents. The stoichiometry and the formation constants of the α-cypermethrin inclusion complexes formed with the CDs were determined. The analytical performances of the PIF method were improved in the presence of HP-β-CD relative to the other media, and a CD-enhanced PIF analytical method was developed. The limits of detection and limits of quantification ranged, respectively, between 6 and 98 ng/mL and between 24 and 343 ng/mL, depending on the medium. Application to the analysis of tap water and Senegal natural water samples collected close to agricultural areas and spiked with α-cypermethrin yielded satisfactory recoveries going from about 77% to 98%. An interference study of foreign species, including pesticides and inorganic ions likely to be present in natural waters, was also carried out. Figure Photolysis reaction of α-cypermethrin in presence of HP-β-CD     

Feasibility on a piezoresistive tactile normal force sensor array

The plasmon resonance of periodic and random arrays of Au-nanodiscs and nano-squares was investigated experimentally and numerically. By randomization, plasmon resonance spectra become broadened, however, the electro-magnetic field enhancement is augmented by a factor of 10–10 $^2$ times at some specific wavelength as shown by the finite-element time-domain calculations. The spatial localization takes place at a fewer hot-spots. The randomized structures are promising for the applications in opto-electronics, sensing and light harvesting.     

Elasticity of ion stuffing in chemically strengthened glass

The chemical strengthening of glass involves the stuffing of large ions into network sites previously occupied by smaller ions. Typically this involves an exchange of Li⁺ or Na⁺ ions in the glass for larger K⁺ ions from a molten salt bath. This swapping of ions creates compressive stress in the surface of the glass, significantly increasing the strength of the final glass product. The magnitude of this compressive stress is governed by the linear network dilation coefficient (LNDC), which defines the amount of linear strain per unit of ion substitution. However, the amount of strain attainable through ion exchange is much smaller compared to what is expected from as-melted versions of the same final glass composition. This effect, which we have termed the “network dilation anomaly,” is a result of the different local environment around the invading ion species in as-melted versus ion-exchanged glasses. A remaining question concerns the nature of the network strain due to ion stuffing. Using molecular dynamics simulations, we show that the strain induced by ion stuffing is entirely elastic. In other words, when a reverse ion exchange is performed to swap the original ions back into the glass, the initial volume of the as-melted glasses is entirely recovered. Moreover, we show that the local structural environment around the alkali ions is restored to the as-melted conditions. The elastic nature of ion stuffing demonstrates that the network dilation anomaly is not a result of plasticity, but rather a failure to achieve the full amount of expected elastic strain during ion exchange. The elasticity itself consists of both instantaneous and delayed contributions.     

Palladium-catalysed direct arylation of a tris-cyclometallated Ir(III) complex bearing 2,2'-thienylpyridine ligands: a powerful tool for the tuning of luminescence properties

Palladium-catalysed direct 5-arylation of metallated thiophenes of fac-Ir(N^C(3')-thpy)(3) with aryl bromides via C-H bond functionalisation allows the synthesis of a variety of new Ir complexes in only one step (thpyH = 2,2'-thienylpyridine). The method offers simple modification of the nature of the ligand and hence of the photophysical properties of such complexes.