Rhodium and iridium complexes of N-heterocyclic carbenes: Structural investigations and their catalytic properties in the borylation reaction

Bridged and unbridged N-heterocyclic carbene (NHC) ligands are metalated with [Ir/Rh(COD)₂Cl]₂ to give rhodium(I/III) and iridium(I) mono- and biscarbene substituted complexes. All complexes were characterized by spectroscopy, in addition [Ir(COD)(NHC)₂][Cl,I] [COD = 1,5-cyclooctadiene, NHC =  1,3-dimethyl- or 1,3-dicyclohexylimidazolin-2-ylidene] (1, 4), and the biscarbene chelate complexes 12 [(η⁴-1,5-cyclooctadiene)(1,1′-di-n-butyl-3,3′-ethylene-diimidazolin-2,2′-diylidene)iridium(I) bromide] and 14 [(η⁴-1,5-cyclooctadiene)(1,1′-dimethyl-3,3′-o-xylylene-diimidazolin-2,2′-diylidene)iridium(I) bromide] were characterized by single crystal X-ray analysis. The relative σ-donor/π-acceptor qualities of various NHC ligands were examined and classified in monosubstituted NHC-Rh and NHC-Ir dicarbonyl complexes by means of IR spectroscopy. For the first time, bis(carbene) substituted iridium complexes were used as catalysts in the synthesis of arylboronic acids starting from pinacolborane and arene derivatives.     

Inhibition of energy transfer between conjugated polymer chains in host/guest nanocomposites generates white photo- and electroluminescence

The generation of white light requires the combination of two or more chromophores that emit simultaneously. The observed color of a mixture of light-emitting molecules, however, originates generally only from the lowest band-gap species because of efficient energy transfer between the chromophores which is difficult to avoid. Here we report on a nanocomposite material designed to yield pure and stable white photo- and electroluminescence. In this material, red, green, and blue emitting conjugated polymers are confined within the galleries of a layered semiconducting host matrix. The host hinders polymer pi-pi interactions which are responsible for the energy transfer between polymer chains, consequently, emission from the three chromophores is observed simultaneously resulting in white photoluminescence. The efficacy of the nanocomposites is demonstrated in simple single-layer white-emitting polymer diodes. The mechanism suggested here for white light generation, supported by extensive luminescence measurements, is in contrast to that previously reported in white-emitting polymer diodes where efficient energy transfer between polymer chains was essential for obtaining white light.     

Band-edge-induced Bragg diffraction in two-dimensional photonic crystals

Two-dimensional photonic crystals composed of two orthogonal volume diffraction gratings have been photogenerated in photopolymers. When the read beam is set at the Bragg angle, the diffraction efficiency of the transmission grating is strongly enhanced at the band edge of the reflection grating recorded in the material. Such a device provides Bragg operation and enhancement of the diffraction efficiency of the thin diffraction grating together with good wavelength selectivity. Such advantages could be interesting for optical signal processing.     

Hetero‐Multifunctional Poly(ethylene glycol) Copolymers with Multiple Hydroxyl Groups and a Single Terminal Functionality

Hetero‐multifunctional poly(ethylene glycol‐co‐glycerol) random copolymers with multiple hydroxyl functionalities and a single terminal functionality have been prepared by copolymerization of ethylene oxide (EO) and ethoxy ethyl glycidyl ether (EEGE) with the use of a suitable initiator, introducing a protected amino group or a double bond, respectively. Acidic deprotection was used for removal of the acetal protecting groups in the chain, and the terminal amino group was regenerated by catalytic hydrogenation. A series of copolymers with narrow polydispersity was obtained, varying comonomer fractions from 3 to 67% and molecular weights in the range of 5 000–32 000 g · mol⁻¹ (1.05 < < 1.25). Molecular and thermal characterization was carried out using ¹H‐ and ¹³C NMR, SEC and differential scanning calorimetry (DSC).

     

A Road Less Traveled to Functional Polymers: Epoxide Termination in Living Carbanionic Polymer Synthesis

Functional polymers possess tremendous potential both in academia and in industry. In particular, oxiranes offer manifold possibilities for the introduction of single hydroxyl or multiple orthogonal functionalities in carbanionic polymerization. Here, we present a brief overview of the fascinating possibilities arising from the employment of common as well as individually designed epoxide derivatives for the synthesis of end‐functional polymers. Continuous flow techniques can be utilized for the rapid generation and screening of precisely defined hydroxyl‐modified polymers. The utilization of functionalized polymers as precursors for the formation of complex macromolecular architectures (e.g., miktoarm star polymers) is summarized and potential applications as well as future perspectives are discussed.

     

Hyperbranched PEG by Random Copolymerization of Ethylene Oxide and Glycidol

The synthesis of hyperbranched poly(ethylene glycol) (hbPEG) in one step was realized by random copolymerization of ethylene oxide and glycidol, leading to a biocompatible, amorphous material with multiple hydroxyl functionalities. A series of copolymers with moderate polydispersity ( < 1.8) was obtained with varying glycidol content (3–40 mol‐%) and molecular weights up to 49 800 g mol⁻¹. The randomly branched structure of the copolymers was confirmed by ¹H and ¹³C NMR spectroscopy and thermal analysis (differential scanning calorimetry). MTS assay demonstrated low cell toxicity of the hyperbranched PEG, comparable to the highly established linear PEG.

     

Enantioselective Titanium(III)-Catalyzed Reductive Cyclization of Ketonitriles

Reduction, please! The title reaction affords α-hydroxyketones, a common structural motif in biologically active natural products, in good yields and high enantioselectivities at room temperature. The commercially available ansa-titanocene 1 was found to be an efficient catalyst for this process, which presumably proceeds by addition of a ketyl radical to a nitrile.     

Analysis of elliptically polarized maximally entangled states for bell inequality tests

When elliptically polarized maximally entangled states are considered, i.e., states having a non random phase factor between the two bipartite polarization components, the standard settings used for optimal violation of Bell inequalities are no longer adapted. One way to retrieve the maximal amount of violation is to compensate for this phase while keeping the standard Bell inequality analysis settings. We propose in this paper a general theoretical approach that allows determining and adjusting the phase of elliptically polarized maximally entangled states in order to optimize the violation of Bell inequalities. The formalism is also applied to several suggested experimental phase compensation schemes. In order to emphasize the simplicity and relevance of our approach, we also describe an experimental implementation using a standard Soleil-Babinet phase compensator. This device is employed to correct the phase that appears in the maximally entangled state generated from a type-II nonlinear photon-pair source after the photons are created and distributed over fiber channels.     

Validity of the law of mass action in three-dimensional coagulation processes

Diffusion-limited reactions are studied in detail on the classical coalescing process. We demonstrate how, with the aid of a recent renormalization group approach, fluctuations can be integrated systematically. We thereby obtain an exact relation between the microscopic physics (lattice structure and particle shape and size) and the macroscopic decay rate in the law of mass action. Moreover, we find a strong violation of the law of mass action. The corresponding term in the kinetic equations originates in long-wavelength fluctuations and is a universal function of the macroscopic decay rate.     

Near-infrared dual luminescence from an extended zinc porphyrin

The photophysical characterization of an extended zinc porphyrin is reported. Fusion of bis-tetraazaanthracene on the porphyrin ring causes an unusual dual luminescence ascribed to two non-equilibrated singlet excited states.