Photochemical C−H Amination of Ethers and Geminal Difunctionalization Reactions in One Pot

A mild, atom‐economic, and metal‐free α‐C?H amination of ethers using relatively stable nonafluorobutanesulfonyl (nonaflyl, Nf) azide as the aminating reagent to give N‐sulfonyl hemiaminals is reported. This enables unprecedented C(sp³) difunctionalization reactions, leading to diverse functionalized amino group containing compounds starting from simple ethers in one pot.     

Analysis of solvent‐accessible voids and proton‐coupled electron transfer of 2,6‐bis(1H‐imidazol‐2‐yl)pyridine and its hydrochloride

The crystal structures of the solid form of solvated 2,6‐bis(1H‐imidazol‐2‐yl)pyridine (H₂dimpy) trihydrate, C₁₁H₉N₅·3H₂O·[+solvent], I , and its hydrate hydrochloride salt 2‐[6‐(1H‐imidazol‐2‐yl)pyridin‐2‐yl]‐1H‐imidazol‐3‐ium chloride trihydrate, C₁₁H₁₀N₅⁺·Cl^?·3H₂O, II , are reported and analysed in detail, along with potentiometric and spectrophotometric titrations for evaluation of the acid–base equilibria and proton‐coupled electron‐transfer reactions. Compound I crystallizes in the high‐symmetry trigonal space group P3₂21 with an atypical formation of solvent‐accessible voids, as a consequence of the 3₂ screw axis in the crystallographic c‐axis direction, which are probably occupied by uncharacterized disordered solvent molecules. Additionally, the trihydrated chloride salt crystallizes in the conventional monoclinic space group P2₁/c without the formation of solvent‐accessible voids. The acid–base equilibria of H₂dimpy were studied by potentiometric and spectrophotometric titrations, and the results suggest the formation of H₃dimpy⁺ (pK_a1 = 5.40) and H₄dimpy²⁺ (pK_a2 = 3.98), with the electrochemical behaviour of these species showing two consecutive irreversible proton‐coupled electron‐transfer reactions. Density functional theory (DFT) calculations corroborate the interpretation of the experimental results and support the assignment of the electrochemical behaviour.     

rac-[CH2(3-tert-butyl-1-indenyl)2]ZrCl2/MAO in the Copolymerization of Olefins and Dienes

Olefin-diene copolymerizations in the presence of C₂ symmetric zirconocene rac-[CH₂(3-tert-butyl-1-indenyl)₂]ZrCl₂/MAO catalytic system have been reported and rationalized by experimental and molecular modeling studies. Ethene gives 1,2-cyclopropane and 1,2-cyclopentane, 1,3-cyclobutane, and 1,3-cyclopentane units in copolymerization with 1,3-butadiene, 1,4-pentadiene, and 1,5-hexadiene, respectively. Propene-1,3-butadiene copolymerizations lead to 1,2 and 1,4 butadiene units and to a low amount of 1,2-cyclopropane units.     

Stereoselective cyclopropanation by cyclocopolymerization of butadiene

An unprecedented cyclopropanation by cyclopolymerization reaction is presented. In particular, catalytic copolymerization processes of ethene and butadiene lead with high trans selectivity to a complete cyclocopolymerization of butadiene units. Ethene-based copolymers including cyclopropane and cyclopentane rings, which can be relevant to polyolefin applications, are obtained with high yields. Several aspects relative to the mechanism of this cyclocopolymerization reaction, including the high stereoselectivity, are discussed.     

A high power high energy pure N2 laser in the first and second positive systems

Simultaneous high energy lasing in the N₂ first and second positive systems is reported. 20.5 mJ (1.5 MW) UV and 5 mJ (0.4 MW) IR laser pulses were produced in pure N₂. The design is open and easy to improve.     

Geodesics,soap bubbles and pattern formation in riemannian surfaces

We study a singularly perturbed semi-linear elliptic PDE with a bistable potential on a closed Riemannian surface. We show that the transition region converges in the sense of varifolds to an embedded (multiple) curve with constant geodesic curvature.     

Geometrical and energetical feasibility of a highly extended chain conformation for isotactic polystyrene

Highly extended, four-atom helices with $\text{h = 5.1}\text{A}\text{?}$ and t = 60° are geometrically feasible for a vinyl polymer. The energetical feasibility for the case of isotactic polystyrene (in crystalline gels) is discussed on the basis of appropriate conformational maps.     

Fast local intensity fluctuations in a pulsed untuned dye laser

Intensity fluctuations in a pulsed dye laser are studied. Fluctuations are local and very fast. The onset of the fluctuating regime coincides with the laser threshold. The average Fourier spectrum of fluctuations shows three broad peaks at frequencies v ₁=55 MHz, v ₂=110 MHz, v ₃=165 MHz. The three frequencies remain unchanged when resonator geometrical and optical parameters are changed. Nevertheless the amplitude of fluctuations is easily affected by such changes and by the solution temperature. The application of the Grassberger-Procaccia algorithm to the experimental fluctuations gives slope convergence (between 3 and 5) in some cases. This seems to indicate that the origin of fluctuations is chaotic-deterministic.