Synthesis and reactivity of uranium(IV) amide complexes supported by a triamidotriazacyclononane ligand

Reaction of [U{(SiMe2NPh)3-tacn}Cl] with LiNEt2 or LiNPh2 affords the corresponding amide compounds, [U{(SiMe2NPh)3-tacn}(NR2)] (R = Et (1), R = Ph (2)). The complexes have been fully characterized by spectroscopic methods and the solid-state structure of 1 was determined by single-crystal X-ray diffraction analysis. The six nitrogen atoms of the tris(dimethylsilylanilide)triazacyclononane ligand are in a trigonal prismatic configuration with the nitrogen atom of the diethylamide ligand capping one of the trigonal faces of the trigonal prism. Crystallization of 2 from CH3CN solution gave crystals of the six-membered heterocycle [U{(SiMe2NPh)3-tacn}{kappa2-(HNC(Me))2CC[triple bond]N}] (3). The reactivity of the amides was investigated. Both compounds undergo acid-base reactions with protic substrates such as HOC6H2-2,4,6-Me3, 3,5-Me2pzH (pz = pyrazolyl) and HSC5H4N to give the corresponding [U{(SiMe2NPh)3-tacn}X] (X = OC6H2-2,4,6-Me3 (4), 3,5-Me2pzH (5), kappa2-SC5H4N (6)) complexes. The solid-state structures of and were determined by single-crystal X-ray diffraction and revealed that the compounds are eight-coordinate with dodecahedral geometry.     

Functionalisation of fluorescent BODIPY dyes by nucleophilic substitution

The BODIPY chromophore can be easily modified by nucleophilic mono- or disubstitution of 3,5-dichloroBODIPY with O-, N-, S- and C-nucleophiles. Absorption and fluorescence spectral data of the new BODIPY derivatives are also reported.     

Synthesis of mixed sequence borane phosphonate DNA

A novel solid-phase phosphoramidite-based method has been developed for the synthesis of borane phosphonate DNA. Keys to this new approach are replacement of the common 5'-dimethoxytrityl blocking group with a 5'-silyl ether and the use of new protecting groups on the bases (adenine, N6-dimethoxytrityl; cytosine, N4-trimethoxytrityl; guanine, N2-[9-fluorenylmethoxycarbonyl]; thymine, N3-anisoyl). Because of these developments, it is now possible for the first time to synthesize oligodeoxynucleotides having any combination of the four 2'-deoxynucleosides and both phosphate and borane phosphonate internucleotide linkages (including oligomers having exclusively borane phosphonate linkages).     

Détonabilité de mélanges stoechiométriques méthane–hydrogène–oxygène–azoteDetonation characteristics of stoichiometric mixtures of methane–hydrogen–oxygen–nitrogen

The goal of this Note is to determine the influence of H₂ addition on the detonation and detonability of stoichiometric CH₄/O₂/N₂ mixtures for three values of the nitrogen dilution $\beta ={\mathrm{N}}_2/{\mathrm{O}}_2$ ($\beta =0$ (oxygen); 2; 3.76 (air)) and also of the influence of the initial temperature. It is based on the measurement of the mean cell size of the steady self-sustained detonation in these mixtures, this characteristic length being representative of the mixture detonability. Results indicate that the detonability of the (CH₄H₂) mixture is mainly controlled by the heavier fuel, i.e., CH₄ and for instance the detonability of the mixture where 20% of CH₄ volume has been replaced by H₂ is nearly the same as that of the mixture where CH₄ is the only fuel. The influence of the initial temperature on the detonability depends on N₂ concentration. To cite this article: C. Matignon et al., C. R. Mecanique 334 (2006).     

Accelerated Electrophotocatalytic C(sp3)−H Heteroarylation Enabled by an Efficient Continuous-Flow Reactor**

Electrophotocatalytic transformations are garnering attention in organic synthesis, particularly for accessing reactive intermediates under mild conditions. Moving these methodologies to continuous-flow systems, or flow ElectroPhotoCatalysis (f-EPC), showcases potential for scalable processes due to enhanced irradiation, increased electrode surface, and improved mixing of the reaction mixture. Traditional methods sequentially link photochemical and electrochemical reactions, using flow reactors connected in series, yet struggle to accommodate reactive transient species. In this study, we introduce a new flow reactor concept for electrophotocatalysis (EPC) that simultaneously utilizes photons and electrons. The reactor is designed with a transparent electrode and employs cost-effective materials. We used this technology to develop an efficient process for electrophotocatalytic heteroarylation of C(sp³)−H bonds. Importantly, the same setup can also facilitate purely electrochemical and photochemical transformations. This reactor represents a significant advancement in electrophotocatalysis, providing a framework for its application in flow for complex synthetic transformations.     

Unimer Exchange Is not Necessary for Morphological Transitions in Polymerization-Induced Self-Assembly

Polymerization-induced self-assembly (PISA) has established itself as a powerful and straightforward method to produce polymeric nano-objects of various morphologies in (aqueous) solution. Generally, spheres are formed in the early stages of polymerization that may evolve to higher order morphologies (worms or vesicles), as the solvophobic block grows during polymerization. Hitherto, the mechanisms involved in these morphological transitions during PISA are still not well understood. Combining a systematic study of a representative PISA system with rheological measurements, we demonstrate that—unexpectedly—unimer exchange is not necessary to form higher order morphologies during radical RAFT-mediated PISA. Instead, in the investigated aqueous PISA, the monomer present in the polymerization medium is responsible for the morphological transitions, even though it slows down unimer exchange.     

Imaging the Footprint of Nanoscale Electrochemical Reactions for Assessing Synergistic Hydrogen Evolution

This work proposes a novel method for measuring the intrinsic activity of single metal-based nanoparticles towards water reduction in neutral media at industrially relevant current densities. Instead of using gas nanobubbles as proxy, the method uses optical microscopy to track the local footprint of the reaction through the precipitation of metal hydroxide, which is associated to the local pH increase during electrocatalysis. The results show the electrocatalytic activities of different types of metal nanoparticles and bifunctionnal core-shell nanostructures made of Ni and Pt, and demonstrate the importance of metal hydroxide nano-shells in enhancing electrocatalysis. This method should be generalizable to any electrocatalytic reaction involving pH changes such as nitrate or CO₂ reduction.