New 3π‐2Spiro Ladder‐Type Phenylene Materials: Synthesis,Physicochemical Properties and Applications in OLEDs

New routes to ladder‐type phenylene materials 1 and 2 are described. The oligomers 1 and 2 , which possess a “3π‐2spiro” architecture, have been synthesized by using extended diketone derivatives 3 and 10 as key intermediates. The physicochemical properties of the new blue‐light emitter 2 were studied in detail and compared with those of the less‐extended 1 . Owing to the recent development of fluorenone derivatives and their corresponding more conjugated analogues as potential electron‐transport materials in organic light‐emitting diodes (OLEDs) and as n‐type materials for photovoltaic applications, we also report herein the thermal, optical and electrochemical behavior of the key intermediates, diketones 3 and 10 . Finally, the application of dispiro 2 as a new light‐emitting material in OLEDs is reported.     

Multilevel parametrization for aerodynamical optimization of 3D shapes

We introduce and discuss a combination of methods and options that aim at the aerodynamical optimization of a flow around an arbitrary aircraft shape. The flow is governed by the Euler equations, discretized by a mixed element-volume method on a fixed unstructured tetrahedrization. The shape parametrization relies on the skin of the above mesh through a hierarchical representation. Descent-type and one-shot algorithms are devised and adapted to the solution of a few model problems.     

Iodide ion promotion of benzyl chloride-borate ester carbonylation reactions

Esters are isolated in fine yields from the rhodium(I) catalyzed reaction of benzyl chlorides with borate esters and carbon monoxide, in the presence of potassium iodide.     

Poincaré-invariant gravitational field and equations of motion of two pointlike objects: The postlinear approximation of general relativity

Using a fast-motion approximation method we obtain the second-order gravitational field and equations of motion for two pointlike objects in algebraically closed form. A regularization procedure is used which is shown to guarantee the consistency of the approximation scheme. The equations of motion are then transformed within the framework of relativistic predictive mechanics into a system of ordinary differential equations.     

‘All‐supramolecular’ Nanocapsules from Low‐Molecular Weight Ureas Through Interfacial Addition Reaction in Miniemulsion

This contribution presents a new strategy for preparing nanocapsules with a shell made of a supramolecular polymer which repeating units are held together by reversible interactions rather than covalent bonds. These nanocapsules were prepared in classical miniemulsion through interfacial addition reaction of a diisocyanate (IPDI) and a monoamine (iBA), forming low‐molecular weight bis‐ureas moieties which are strong self‐complementary interacting molecules through hydrogen‐bonding. The nanocapsules present a diameter around 100 nm, and MALDI‐TOF MS and ¹H NMR analyses confirm the expected molecular characteristics for the shell. This strategy opens the scope of a new type of nanomaterials exhibiting stimuli‐responsiveness due to the reversible interaction linking the repeating units.

     

Exchange and correlation effects in electronic excitations of Cu(2)O

State-of-the-art theoretical methods fail in describing the optical absorption spectrum, band gap, and optical onset of Cu(2)O. We have extended a recently proposed self-consistent quasiparticle approach, based on the GW approximation, to the calculation of optical spectra, including excitonic effects. The band structure compares favorably with our present angle-resolved photoemission measurements. The excitonic effects based on these realistic band structure and screening provide a reliable optical absorption spectrum, which allows for a revised interpretation of its main structures.     

Lithium environment in dilute poly(ethylene oxide)/lithium triflate polymer electrolyte from REDOR NMR spectroscopy

The role of the lithium ion environment is of fundamental interest regarding transport and conductivity in lithium polymer electrolytes. X-ray crystallography has been used to characterize the lithium environment in completely crystalline poly(ethylene oxide) (PEO) electrolytes, but this approach cannot be used with dilute PEO electrolytes. Here, using solid-state NMR data collected with the rotational-echo double-resonance 13C[7Li] (REDOR) pulse sequence, we have been able to characterize the crystalline microdomains of a PEO-lithium triflate sample with an oxygen/lithium ratio of 20:1. Our data clearly demonstrates that the lithium crystalline microdomains are nearly identical to those of a completely crystalline 3:1 sample, for which the crystal structure is known.     

UV photolysis of C4N2 in water ices: new possible route of synthesis of ammonium bicarbonate and ammonium formate

Laboratory experiments involving ultraviolet (UV) irradiation of dicyanoacetylene (C(4)N(2)) trapped in water ice at 10 K have been conducted and monitored by infrared spectroscopy (FTIR). By the support of isotopic experiments and theoretical calculations, the irradiation of a DCA/H(2)O ice mixture at lambda > 230 nm has been found to be a possible source of NH(4)(+)HCO(3)(-) (ammonium bicarbonate) and NH(4)(+)HCOO(-) (ammonium formate). These latter compounds can arise from a proton-transfer reaction between H(2)O and the CN radical, which is issued from photolyzed C(4)N(2).