Search results for "Coupling"
showing 10 items of 1862 documents
Reactivity of Nickel(II) Porphyrins in oCVD Processes—Polymerisation, Intramolecular Cyclisation and Chlorination
2019
Abstract Oxidative chemical vapour deposition of (5,15‐diphenylporphyrinato)nickel(II) (NiDPP) with iron(III) chloride as oxidant yielded a conjugated poly(metalloporphyrin) as a highly coloured thin film, which is potentially useful for optoelectronic applications. This study clarified the reactive sites of the porphyrin monomer NiDPP by HRMS, UV/Vis/NIR spectroscopy, cyclic voltammetry and EPR spectroscopy in combination with quantum chemical calculations. Unsubstituted meso positions are essential for successful polymerisation, as demonstrated by varying the porphyrin meso substituent pattern from di‐ to tri‐ and tetraphenyl substitution. DFT calculations support the proposed radical oxi…
The 1-way on-line coupled atmospheric chemistry model system MECO(n) – Part 3: Meteorological evaluation of the on-line coupled system
2012
Abstract. Three detailed meteorological case studies are conducted with the global and regional atmospheric chemistry model system ECHAM5/MESSy(→COSMO/MESSy)n, shortly named MECO(n), in order to assess the general performance of the on-line coupling of the regional model COSMO to the global model ECHAM5. The cases are characterised by intense weather systems in Central Europe: an intense cold frontal passage in March 2010, a convective frontal event in July 2007, and the high impact winter storm "Kyrill" in January 2007. Simulations are performed with the new on-line-coupled model system and compared to classical, off-line COSMO hindcast simulations driven by ECMWF analyses. Precipitation o…
C−C Cross-Couplings from a Cyclometalated Au(III) C∧ N Complex: Mechanistic Insights and Synthetic Developments
2021
Abstract In recent years, the reactivity of gold complexes was shown to extend well beyond π‐activation and to hold promises to achieve selective cross‐couplings in several C−C and C−E (E=heteroatom) bond forming reactions. Here, with the aim of exploiting new organometallic species for cross‐coupling reactions, we report on the Au(III)‐mediated C(sp2)−C(sp) occurring upon reaction of the cyclometalated complex [Au(CCH2N)Cl2] (1, CCH2N=2‐benzylpyridine) with AgPhCC. The reaction progress has been monitored by NMR spectroscopy, demonstrating the involvement of a number of key intermediates, whose structures have been unambiguously ascertained through 1D and 2D NMR analyses (1H, 13C, 1H‐1H CO…
One-dimensional oxalato-bridged copper(II) complex possessing two structurally different metallic centres
2001
Abstract The crystal structure of the oxalato-bridged copper(II) compound [Cu2(μ-ox)2(ampy)3]n 1 (ox=oxalate dianion, ampy=2-amino-3-methylpyridine) consists of infinite corrugated one-dimensional chains in which two types of copper(II) centres, five- and six-coordinated, are bridged sequentially by asymmetric bis-bidentate oxalato ligands. Magnetic susceptibility measurements show the occurrence of a significant intrachain antiferromagnetic coupling (J=−22.9 cm −1 ) .
Accurate tuning of mismatched twin-core fiber filters
1998
We have demonstrated a reproducible and accurate way of tuning the coupling wavelength of a mismatched twin-core filter. This method allows high quality all-fiber filters to be implemented with low loss at any desired wavelength over a range of few hundred nanometers from the same fiber. An ~500-nm tuning range is demonstrated, limited only by the measurement setup and not by the technique itself. Highly accurate control of the filtering wavelength in combination with control of filtering strength by adjustment of the length of the twin-core fibers allows complex filter profiles to be implemented by cascading of several different filters. These filters are also very stable to a change in te…
Primordial dark matter from curvature induced symmetry breaking
2020
We demonstrate that adiabatic dark matter can be generated by gravity induced symmetry breaking during inflation. We study a $Z_2$ symmetric scalar singlet that couples to other fields only through gravity and for which the symmetry is broken by the spacetime curvature during inflation when the non-minimal coupling $\xi$ is negative. We find that the symmetry breaking leads to the formation of adiabatic dark matter with the observed abundance for the singlet mass $m\sim{\rm MeV}$ and $|\xi|\sim 1$.
Black Hole Shadow Drift and Photon Ring Frequency Drift
2021
The apparent angular size of the shadow of a black hole in an expanding Universe is redshift-dependent. Since cosmological redshifts change with time - known as the redshift drift - all redshift-dependent quantities acquire a time-dependence, and a fortiori so do black hole shadows. We find a mathematical description of the black hole shadow drift and show that the amplitude of this effect is of order $10^{-16}$ per day for M87$^{\star}$. While this effect is small, we argue that its non-detection can be used to constrain the accretion rate around supermassive black holes, as well as a novel probe of the equivalence principle. If general relativity is assumed, we infer from the data obtaine…
Despicable dark relics: generated by gravity with unconstrained masses
2019
We demonstrate the existence of a generic, efficient and purely gravitational channel producing a significant abundance of dark relics during reheating after the end of inflation. The mechanism is present for any inert scalar with the non-minimal curvature coupling $\xi R\chi^2$ and the relic production is efficient for natural values $\xi = {\cal O}(1)$. The observed dark matter abundance can be reached for a broad range of relic masses extending from $m \sim 1 {\rm k eV}$ to $m \sim 10^{8} {\rm GeV}$, depending on the scale of inflation and the dark sector couplings. Frustratingly, such relics escape direct, indirect and collider searches since no non-gravitational couplings to visible ma…
ChemInform Abstract: Enantioselective Palladium-Catalyzed Oxidative β,β-Fluoroarylation of α,β-Unsaturated Carbonyl Derivatives.
2016
The site-selective palladium-catalyzed three-component coupling of deactivated alkenes, arylboronic acids, and N-fluorobenzenesulfonimide is disclosed herein. The developed methodology establishes a general, modular, and step-economical approach to the stereoselective β-fluorination of α,β-unsaturated systems.
Synthesis of Highly Fluorinated 2,2′-Biphenols and 2,2′-Bisanisoles
2010
Multiply fluorine-substituted iodo anisoles are efficiently coupled in an Ullmann-type reaction to provide the corresponding bisanisoles. The coupling is selective and even tolerates bromo moieties. Subsequent deprotection of hydroxy groups gives access to highly fluorinated biphenols.