Functionalized poly(oxanorbornene)‐block‐copolymers: Preparation via ROMP/click‐methodology

Block copolymers on basis of poly(oxanorbornenes) bearing functional moieties in their side‐chains are prepared via a combination of ROMP‐methods and 1,3‐dipolar‐“click”‐reactions. Starting from N‐substituted‐ω‐bromoalkyl‐oxanorbornenes and alkyl‐/perfluoroalkyl‐oxanorbornenes, block copolymers with molecular weights up to 25,000 g mol^?1 were generated. Subsequent nucleophilic exchange‐reactions yielded the block‐copolymers functionalized with ω‐azidoalkyl‐moieties in one block. The 1,3‐azide/alkine‐“click” reactions with a variety of terminal alkynes in the presence of a catalyst system consisting of tetrakis(acetonitrile)hexafluorophosphate copper(I) and tris(1‐benzyl‐5‐methyl‐1H‐ [1,2,3]triazol‐4‐ylmethyl)‐amine furnished the substituted block copolymers in high yields, as proven by NMR‐spectroscopy. The resulting polymers were investigated via temperature‐dependent SAXS‐methods, revealing their microphase separated structure as well as their temperature‐dependent behavior. The presented method offers the generation of a large set of different block‐copolymers from only a small set of starting materials because of the high versatility of the “click” reaction, thus enabling a simple and complete functionalization after the initial polymerization reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 485–499, 2007     

Luminescent copolymers for applications in multicolor‐light‐emitting devices

Light‐emitting diodes based on organic materials [organic light‐emitting diodes (OLEDs)] have attracted much interest over the past decade. Several different attempts have been made to realize multicolor OLEDs. This article describes a new approach based on energy transfer in a donor/acceptor system. A copolymer containing both donor and acceptor compounds as comonomer units is prepared. The polymer consists of a derivative of a luminescent dye [4‐dicyanmethylene‐2‐methyl‐6‐4H‐pyran (DCM); acceptor compound], which is copolymerized with fluorene (donor compound) to combine the properties of an electroactive polymer with a highly luminescent dye. Photochemical processing is achieved by UV irradiation of this copolymer in the presence of gaseous trialkylsilanes. This reagent selectively saturates the C?C bonds in the DCM comonomer units while leaving the fluorene units essentially unaffected. As a result of the photochemical process, the red electroluminescence of the acceptor compound vanishes, and the blue‐green electroluminescence from the polyfluorene units is recovered. Compared with previous approaches based on polymer blends, this copolymer approach avoids problems associated with phase‐separation phenomena in the active layer of OLEDs. © 2006Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4317–4327, 2006     

Performance analysis of 1300 nm SLEDs – impact of temperature and length scaling

The impact of self-heating and cavity length on the spectral emission properties of SLEDs is investigated using a state-of-the-art simulation tool. Simulated data are compared to measurements for two InP-based benchmark devices operating around 1300 nm, and excellent agreement is achieved in either case.     

Radiation conditions and uniqueness for stationary oscillations in elastic plates

Sommerfeld-type radiation conditions are indicated for the solutions of the system governing the small stationary oscillations in plates with transverse shear deformation, and a uniqueness theorem is proved in the case of the corresponding exterior Dirichlet and Neumann problems.

     

Kinetic limit of a conservative lattice gas dynamics showing long-range correlations

An anisotropic lattice gas dynamics is investigated for which particles on ^d jump to empty nearest neighbor sites with (fast) rate ^–2 in a specified direction and some particular configuration-dependent rates in the other directions. The model is translation and reflection invariant and is particle conserving. The space coordinate in the fast-rate direction is rescaled by ^–1. It follows that the density field converges in probability, as 0, to the corresponding solution of a nonlinear diffusion-type equation. The microscopic fluctuations about the deterministic macroscopic evolution are determined explicitly and it is found that the stationary fluctuations decay via a power law (1/r ^d ) with the direction dependence of a quadrupole field.     

Statistical mechanics of probabilistic cellular automata

We investigate the behavior of discrete-time probabilistic cellular automata (PCA), which are Markov processes on spin configurations on ad-dimensional lattice, from a rigorous statistical mechanics point of view. In particular, we exploit, whenever possible, the correspondence between stationary measures on the space-time histories of PCAs on ^d and translation-invariant Gibbs states for a related Hamiltonian on ( ^d+1). This leads to a simple large-deviation formula for the space-time histories of the PCA and a proof that in a high-temperature regime the stationary states of the PCA are Gibbsian. We also obtain results about entropy, fluctuations, and correlation inequalities, and demonstrate uniqueness of the invariant state and exponential decay of correlations in a high-noise regime. We discuss phase transitions in the low-noise (or low-temperature) regime and review Toom's proof of nonergodicity of a certain class of PCAs.     

Fe(CO)5 thin films adsorbed on Au(111) and on self-assembled organic monolayers: I. Structure

The adsorption of Fe(CO)(5) onto Au(111)/mica and C(4), C(8), C(12), and C(16) SAMs/Au(111)/mica surfaces has been studied using infrared spectroscopy to elucidate the coverage-dependent structures of these films and the intermolecular couplings that determine the form of the spectra. For all substrates, the first layer is composed of molecules physisorbed with one axial and two equatorial carbonyl groups directed toward the substrate; subsequent layers are preferentially oriented with the C(3) molecular axis aligned perpendicular to the substrate (i.e., one axial carbonyl group directed toward the substrate). The axial vibrational band systematically shifts to higher frequencies with increasing surface coverage because of the effects of intermolecular coupling of the quasiparallel transition dipole moments. The strong effects of dipolar coupling are also witnessed by the trends of the band positions when the distance to the image plane is systematically varied using highly organized self-assembled organic substrates; no band shifts are observed when dilute Fe(CO)(5) is embedded in Xe matrixes under identical experimental conditions. The as-deposited films are structurally stable below 125 K on Au(111)/mica surfaces and below 100 K on the organic self-assembled monolayers. The instability of the films above these temperatures demonstrates that the as-adsorbed films do not form thermodynamically well-defined phases but are structurally metastable. The results presented herein and in the companion paper provide a consistent framework to interpret the spectroscopy of these systems that resolves outstanding issues concerning these films and provides a structural model that explains the dynamic properties of these films during exposure to low-energy electron beams.     

Synthesis of some substituted 3-alkenyl-1-phenylpyrazoles

The regioselective synthesis of new 3-alkenyl-1-phenylpyrazoles 4 from the reaction of phenylhydrazine with 2,3-dihydro-4H-pyran-4-ones 1 is described.