The two spin states of an end-on copper(II)-superoxide mimic

The reaction of nitrosobenzene with copper(I) complexes of a tetradentate ligand led to two novel species that are best described as copper(II) complexes of an O-bonded nitrosobenzyl radical anion, in either the singlet or the triplet spin-state. Both states were characterized by crystal structures, magnetic measurements and DFT calculations.     

A novel ruthenium(II) complex for two-photon absorption-based optical power limiting in the near-IR range

In this article, the synthesis of a novel high-conjugated ligand and its corresponding Ru(II) complex PTFTF:Ru is reported, along with the linear and nonlinear optical characterizations. Two-photon absorption based optical power limiting properties (OPL), especially in the near infrared, are described and compared to those of the analogous complexes previously published. Combined with a preliminary theoretical approach, this allows us to highlight several key parameters for OPL optimization in such molecular systems and more particularly the spectral overlap between TPA and excited-state absorption.     

The C-Cl···π interactions inside supramolecular nanotubes of hexaethynylhexamethoxy[6]pericyclyne

Model complexes of hexaethynylhexamethoxy[6]pericyclyne (HM6P) molecules, with or without dichloromethane (DCM) guests, have been calculated at the M05-2X/6-311G(d,p) DFT level. Analysis of nonbonding interactions shows that the cohesion of the supramolecular tubular assemblies previously observed in the crystal state, relies mainly on C-H···O hydrogen bonds between axial ethynyl and equatorial methoxy substituents of stacked HM6P C(18) macrocycles in a cyclohexane-like chair conformation. The intrinsic binding energy of one HM6P molecule with two neighbors is calculated to be more than 40 kcal mol(-1). The inner channel of the stacks (of ca. 8 ? diameter) are suitable for hosting DCM molecules. Using the Atoms In Molecules (AIM) theory, the interaction between DCM molecules and surrounding triple bonds is analyzed in terms of σ-hole-directed C-Cl···π halogen bonds. A σ-hole-directed Cl···Cl interaction between two chlorine atoms of different DCM molecules is also evidenced.     

Euclidean algorithms are Gaussian

We obtain a central limit theorem for a general class of additive parameters (costs, observables) associated to three standard Euclidean algorithms, with optimal speed of convergence. We also provide very precise asymptotic estimates and error terms for the mean and variance of such parameters. For costs that are lattice (including the number of steps), we go further and establish a local limit theorem, with optimal speed of convergence. We view an algorithm as a dynamical system restricted to rational inputs, and combine tools imported from dynamics, such as transfer operators, with various other techniques: Dirichlet series, Perron's formula, quasi-powers theorems, and the saddle-point method. Such dynamical analyses had previously been used to perform the average-case analysis of algorithms. For the present (dynamical) analysis in distribution, we require estimates on transfer operators when a parameter varies along vertical lines in the complex plane. To prove them, we adapt techniques introduced recently by Dolgopyat in the context of continuous-time dynamics (Ann. Math. 147 (1998) 357).     

Nitroxide‐mediated homo‐ and block copolymerization of styrene and multifunctional acryl‐ and methacryl derivatives

The ability of different alkoxyamines ( I1 , I2 , I3 , I4 , and I5 ) to initiate controlled radical polymerization of styrene was evaluated. Among them, 2‐hydroxymethyl‐2‐[(2‐methyl‐1‐phenyl‐propyl)‐(1‐phenyl‐ethoxy)‐amino]‐propane‐1,3‐diol ( I5 ) gave the highest polymerization rate of styrene, and the best control over the molecular weight and the molecular weight distribution of polystyrene. Kinetic studies confirmed that with initiator I5 the polymerization of styrene proceeded in a controlled way. The controlled radical homopolymerization of multifunctional acryl‐ and methacryl derivatives using initiator I5 could not be realized as demonstrated by the high polydispersities (PD) obtained. However, it was possible to polymerize multifunctional acryl‐ and methacryl derivatives using a polystyrene macroinitiator ( Pst ) and, thus, novel amphiphilic block copolymers with a narrow molecular weight distribution were obtained. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1873–1882, 2005     

Synthesis and spectroscopic properties of monocyclic and bicyclic erbium phtalocyanines

Bimacrocyclic and monomacrocyclic erbium phtalocyanines have been synthesized and their luminescence spectra and lifetimes have been studied. The bi-planar structure of ErPc₂ complexes, although interesting at first sight, is non-luminescent because of a strong absorption band near 1.5 μm. However, the luminescence of the erbium ion can be recovered after oxidation or reduction of the macrocycle. Monomacrocyclic erbium phtalocyanines exhibit a strong luminescence of erbium as a result of the energy transfer between the excited phtalocyanine macrocycle and the erbium ion. With a perchlorinated phtalocyanine and a perdeuterated axial ligand in a deuterated solvent, the luminescence lifetime reaches 5 μs, which is the maximum lifetime found for conventional perdeutarated ligands. The large absorption cross-section of phtalocyanine in the red may counterbalance the fast luminescence lifetime, allowing the hope for a new all-organic integrated optical amplifier device.     

A 100-kW three-phase AC plasma furnace for spheroidization of aluminum silicate particles

A 100-kW three-phase ac plasma furnace with sheathed copper electrodes (sheathing gas: air) is presented. It is used for spheroidizing chamotte (refractory-fired clay) particles having a smooth, pore-free surface. A simple, one-dimensional numerical model for the heat transfer to the particles explains the maximum processing rate and the detrimental influence of an inhomogeneous particle size distribution.