Unprecedented Double aza‐Michael Addition within a Sapphyrin Core

A novel sapphyrin derivative was obtained from the reaction between a free‐base sapphyrin and dimethyl acetylenedicarboxylate (DMAD). The formation of the new compound involved a double aza‐Michael addition of two pyrrolic NH groups to a DMAD molecule, with the formation of a disubstituted ethano bridge. The NMR spectral data reveal a product with an unsymmetrical structure; DFT calculations provided support for a structure in which the ethano bridge links two adjacent pyrrole units. The present study provides a seemingly unprecedented example of an N,N′‐dinucleophile reacting with DMAD to form a heterocyclic compound in which the two N‐atoms are linked to the two sp³ carbon atoms derived from a substituted acetylene.     

Stereoselective Csp3–Csp2 Bond‐Forming Reactions by Transition‐Metal‐Free Reductive Coupling of Cyclic Tosylhydrazones with Boronic Acids

The reactions between alkenylboronic acids and tosylhydrazones derived from substituted cyclohexanones lead to the construction of disubstituted cyclohexanes with total regio‐ and stereoselectivity. In these transition‐metal‐free processes, a Csp³?Csp² and Csp³?H bond are formed on the same carbon atom. The stereoselective reaction is general for 2‐, 3‐, and 4‐substituted cyclohexanone tosylhydrazones, as well as for 2‐substituted cyclopentanones. However, no stereoselectivity is observed for acyclic derivatives. DFT computational modeling suggests that the stereoselectivity of the reaction is determined by the approach of the boronic acid to the diazocyclohexane on its most stable chair conformation through an equatorial trajectory.     

Large N‐Heteroacenes: New Tricks for Very Old Dogs?

Azaacenes have been known for a very long time, either as N,N′‐dihydro compounds or in their oxidized form as 4 n+2π systems, but only recently have processable and charcterizable derivatives been sought. In the last three years synthetic routes to large N‐heteroacenes have been developed. In particular, the Pd‐catalyzed coupling of aromatic diamines with activated aromatic dihalogenides has enabled simple access to numerous new azaacenes. Since 2010, azapentacene and stabile oligoazahexacene have been synthesized, as well as a symmetrical tetraazapentacene, which acts as an excellent electron‐transport material for thin‐film transistors.     

Spin State Tunes Oxygen Atom Transfer towards FeIVO Formation in FeII Complexes

Oxoiron(IV) complexes bearing tetradentate ligands have been extensively studied as models for the active oxidants in non-heme iron-dependent enzymes. These species are commonly generated by oxidation of their ferrous precursors. The mechanisms of these reactions have seldom been investigated. In this work, the reaction kinetics of complexes [Fe^II(CH₃CN)₂L](SbF₆)₂ ( [1](SbF₆)₂ and [2](SbF₆)₂ ) and [Fe^II(CF₃SO₃)₂L] ( [1](OTf)₂ and [2](OTf)₂ ( 1 , L=^Me,HPytacn; 2 , L=^nP,HPytacn; ^R,R′Pytacn=1-[(6-R′-2-pyridyl)methyl]-4,7- di-R-1,4,7-triazacyclononane) with Bu₄NIO₄ to form the corresponding [Fe^IV(O)(CH₃CN)L]²⁺ ( 3 , L=^Me,HPytacn; 4 , L=^nP,HPytacn) species was studied in acetonitrile/acetone at low temperatures. The reactions occur in a single kinetic step with activation parameters independent of the nature of the anion and similar to those obtained for the substitution reaction with Cl⁻ as entering ligand, which indicates that formation of [Fe^IV(O)(CH₃CN)L]²⁺ is kinetically controlled by substitution in the starting complex to form [Fe^II(IO₄)(CH₃CN)L]⁺ intermediates that are converted rapidly to oxo complexes 3 and 4 . The kinetics of the reaction is strongly dependent on the spin state of the starting complex. A detailed analysis of the magnetic susceptibility and kinetic data for the triflate complexes reveals that the experimental values of the activation parameters for both complexes are the result of partial compensation of the contributions from the thermodynamic parameters for the spin-crossover equilibrium and the activation parameters for substitution. The observation of these opposite and compensating effects by modifying the steric hindrance at the ligand illustrates so far unconsidered factors governing the mechanism of oxygen atom transfer leading to high-valent iron oxo species.     

On a parabolic–elliptic chemotactic model with coupled boundary conditions

This paper deals with a nonlinear system of parabolic–elliptic type with a logistic source term and coupled boundary conditions related to pattern formation. We prove the existence of a unique positive global in time classical solution. We also analyze the associated stationary problem. Moreover it is proved, under the assumption of sufficiently strong logistic damping, that there is only one nonzero homogeneous equilibrium, and all the solutions to the nonstationary problem tend to this steady state for large times.     

Optimization of a holographic memory setup using an LCD and a PVA-based photopolymer

Holographic data pages were stored in a polyvinyl alcohol (PVA)/acrylamide (AA) photopolymer. This material is formed of AA photopolymers which are considered interesting materials for recording holographic memories. A liquid crystal device was used to modify the object beam and store the data pages in the material. During the storage process, some parameters like exposure time, beam ratio and reading beam intensity were controlled to obtain high image quality after the reconstruction process. The bit error rate (BER) was calculated fitting the histograms of the images to determine what parameters improve the quality of the images.