Radical one-pot α,β-dual and β-mono-oxymethylation of alkylidenemalonate

Dimethylzinc-mediated radical conjugate addition reaction of dimethyl alkylidenemalonates with iodomethyl pivalate gave a high yield of the α,β-dual oxymethylation product in one pot under air and the β-pivaloyloxymethylation product under argon.     

Are safe results obtained when the PC-SAFT equation of state is applied to ordinary pure chemicals?

The PC-SAFT equation of state is a very popular and promising model for fluids that employs a complicated pressure-explicit mathematical function (and can therefore not be solved analytically at a specified pressure and temperature, contrary to classical cubic equations). In this work, we demonstrate that in case of pure fluids, the PC-SAFT equation may exhibit up to five different volume roots whereas cubic equations give at the most three volume roots (and yet, only one or two volume roots have real significance). The consequence of this strongly atypical behaviour is the existence of two different fluid–fluid coexistence lines (the vapour-pressure curve and an additional liquid–liquid equilibrium curve) and two critical points for a same pure component, which is obviously physically inconsistent. In addition to n-alkanes, nearly 60 very common pure components (branched alkanes, cycloalkanes, aromatics, esters, gases, and so on) were tested out and without any exception, we can claim that all of them exhibit this undesired behaviour. In addition, such similar phenomena (i.e. existence of more than three volume roots) may also arise with mixtures. From a computational point of view, most of the algorithms used for solving equations of state only search for three roots at the most and are thus likely to be inefficient when an equation of state gives more than three volume roots. To overcome this limitation, a simple procedure allowing to identify all the possible volume roots of an equation of state is proposed.     

Variable temperature STM study of Co deposition on a dodecanethiol self assembled monolayer

The present scanning tunneling microscopy study reports on the growth processes of Co vapor-deposited on a dodecanethiol (DDT) self-assembled monolayer (SAM)/Au(111). We observe strongly modified surface and depth diffusions of Co adatoms depending on the growth temperature. Co deposited at 300 K shows an extremely incomplete regime of condensation on the organic layer. Besides, Co penetrates the DDT monolayer and resides at the DDT/Au(111) interface as 2D clusters. This phenomenon takes place through defects in the SAM which are transient channels. In contrast, Co deposited at 50 K shows a complete condensation and nucleates on defects of the SAM layer as 3D islands sitting most likely on top of the DDTs. These results are of interest in the growing field of organic spintronics where the quality of the organic/ferromagnetic interface is a key issue.     

Electrochemical and chemical formation of [Mn4(IV)O5(terpy)4(H2O)2]6+, in relation with the photosystem II oxygen-evolving center model [Mn2(III,IV)O2(terpy)2(H2O)2]3+

To examine the real ability of the binuclear di-mu-oxo complex [Mn2(III,IV)O2(terpy)2(H2O)2]3+ (2) to act as a catalyst for water oxidation, we have investigated in detail its redox properties and that of its mononuclear precursor complex [Mn(II)(terpy)2]2+ (1) in aqueous solution. It appears that electrochemical oxidation of 1 allows the quantitative formation of 2 and, most importantly, that electrochemical oxidation of 2 quantitatively yields the stable tetranuclear Mn(IV) complex, [Mn4(IV)O5(terpy)4(H2O)2]6+ (4), having a linear mono-mu-oxo{Mn2(mu-oxo)2}2 core. Therefore, these results show that the electrochemical oxidation of 2 in aqueous solution is only a one-electron process leading to 4 via the formation of a mono-mu-oxo bridge between two oxidized [Mn2(IV,IV)O2(terpy)2(H2O)2]4+ species. 4 is also quantitatively formed by dissolution of the binuclear complex [Mn2(IV,IV)O2(terpy)2(SO4)2] (3) in aqueous solutions. Evidence of this work is that 4 is stable in aqueous solutions, and even if it is a good synthetic analogue of the "dimers-of-dimers" model compound of the OEC in PSII, this complex is not able to oxidize water. As a consequence, since 4 results from an one-electron oxidation of 2, 2 cannot act as an efficient homogeneous electrocatalyst for water oxidation. This work demonstrates that a simple oxidation of 2 cannot produce molecular oxygen without the help of an oxygen donor.     

A notion of geometric complexity and its application to topological rigidity

We introduce a geometric invariant, called finite decomposition complexity (FDC), to study topological rigidity of manifolds. We prove for instance that if the fundamental group of a compact aspherical manifold M has FDC, and if N is homotopy equivalent to M, then M×ℝ ⁿ is homeomorphic to N×ℝ ⁿ , for n large enough. This statement is known as the stable Borel conjecture. On the other hand, we show that the class of FDC groups includes all countable subgroups of GL(n,K), for any field K.     

Solutions of Δ<Emphasis Type="Italic">u</Emphasis>=4<Emphasis Type="Italic">u</Emphasis><Superscript><Emphasis Type="Italic">2</Emphasis></Superscript> with Neumann’s conditions using the Brownian snake

We consider a Brownian snake (W_s,s0) with underlying process a reflected Brownian motion in a bounded domain D. We construct a continuous additive functional (L_s,s0) of the Brownian snake which counts the time spent by the end points _s of the Brownian snake paths on D. The random measure Z=_sdLs is supported by D. Then we represent the solution v of u=4u² in D with weak Neumann boundary condition 0 by using exponential moment of (Z,) under the excursion measure of the Brownian snake. We then derive an integral equation for v. For small it is then possible to describe negative solution of u=4u² in D with weak Neumann boundary condition . In contrast to the exit measure of the Brownian snake out of D, the measure Z is more regular. In particular we show it is absolutely continuous with respect to the surface measure on D for dimension 2 and 3.Mathematics Subject Classification (2000):60J55, 60J80, 60H30, 60G57, 35C15, 35J65     

Well‐Defined Silica‐Supported Mo–Alkylidene Catalyst Precursors Containing One OR Substituent: Methods of Preparation and Structure–Reactivity Relationship in Alkene Metathesis

Silica supports : Well‐defined silica‐supported Mo–alkylidene complexes containing one alkoxy/aryloxy substituent are selectively obtained by grafting onto silica either well‐defined molecular bis(alkoxy) or alkoxyamido complexes (see scheme). These silica‐supported complexes are highly efficient catalyst precursors for the metathesis of acyclic alkenes. However, they display poor performances in ring‐closing metathesis reactions, possibly due to the relatively large siloxy ligand (silica) inducing a greater rigidity.

     

Modulation of a Supramolecular Figure-of-Eight Strip Based on a Photoswitchable Stiff-Stilbene

The preparation, assembly and dynamic properties of photoswitchable bisphosphine ligands based on the stiff-stilbene scaffold are reported. Directional bonding and coordination-induced assembly allow complexation of these ligands with palladium(II), resulting in the formation of discrete metallo-supramolecular entities. While the Z isomer forms a simple bidentate metallo-macrocycle, an intricate double helicate figure-of-eight dimer is observed with the E ligand. Topologically 3D complexes can thus be obtained from 2D ligands. Upon irradiation with UV light, isomerization of the ligands allows control of the architecture of the formed complexes, resulting in a light-triggered modulation of the supramolecular topology. Furthermore, a mechanistic investigation unveiled the dynamic nature of the helicate chirality, where a transmission of motion from the palladium centers yields an „eight-to-eight“ inversion.     

Self-enhanced multicolor electrochemiluminescence by competitive electron-transfer processes

Controlling electrochemiluminescence (ECL) color(s) is crucial for many applications ranging from multiplexed bioassays to ECL microscopy. This can only be achieved through the fundamental understanding of high-energy electron-transfer processes in complex and competitive reaction schemes. Recently, this field has generated huge interest, but the effective implementation of multicolor ECL is constrained by the limited number of ECL-active organometallic dyes. Herein, the first self-enhanced organic ECL dye, a chiral red-emitting cationic diaza [4]helicene connected to a dimethylamino moiety by a short linker, is reported. This molecular system integrates bifunctional ECL features (i.e. luminophore and coreactant) and each function may be operated either separately or simultaneously. This unique level of control is enabled by integrating but decoupling both molecular functions in a single molecule. Through this dual molecular reactivity, concomitant multicolor ECL emission from red to blue with tunable intensity is readily obtained in aqueous media. This is done through competitive electron-transfer processes between the helicene and a ruthenium or iridium dye. The reported approach provides a general methodology to extend to other coreactant/luminophore systems, opening enticing perspectives for spectrally distinct detection of several analytes, and original analytical and imaging strategies.

Controlling electrochemiluminescence (ECL) color(s) is crucial for many applications ranging from multiplexed bioassays to ECL microscopy.     

Blocking and invasion for reaction–diffusion equations in periodic media

We investigate the large time behavior of solutions of reaction–diffusion equations with general reaction terms in periodic media. We first derive some conditions which guarantee that solutions with compactly supported initial data invade the domain. In particular, we relate such solutions with front-like solutions such as pulsating traveling fronts. Next, we focus on the homogeneous bistable equation set in a domain with periodic holes, and specifically on the cases where fronts are not known to exist. We show how the geometry of the domain can block or allow invasion. We finally exhibit a periodic domain on which the propagation takes place in an asymmetric fashion, in the sense that the invasion occurs in a direction but is blocked in the opposite one.