Iridium Cyclooctene Complex Forms a Hyperpolarization Transfer Catalyst Before Converting to a Binuclear C-H Bond Activation Product Responsible for Hydrogen Isotope Exchange

[IrCl(COE)2]2 ( 1 ) reacts with pyridine and H2 to form crystallo-graphically characterized IrCl(H)2(COE)(py)2 ( 2 ). 2 undergoes pyridine loss to form 16-electron IrCl(H)2(COE)(py) (3) with equivalent hydride ligands. When this reaction is studied with parahydrogen, 1 efficiently achieves the hyperpolarization of free pyridine (and nicotinamide, nicotine, 5-aminopyrimidine and 3,5-lutudine) via signal amplification by reversible exchange (SABRE) and hence reflects a simple and readily available precatayst for this process. 2 reacts further over 48 hrs at 298 K to form crystallographically characterized (Cl)(H)(py)(μ-Cl)(μ-H)(κ-μ-NC5H4)Ir(H)(py)2 (4). This dimer is shown to be active in the hydrogen isotope exchange process that is used in radiophar-maceutical preparations. Furthermore, while [Ir(H)2(COE)(py)3]PF6 ( 6 ) forms on addition of AgPF6 to 2 , its stability precludes its efficient involvement in SABRE

RoboPol: First season rotations of optical polarization plane in blazars

We present first results on polarization swings in optical emission of blazars obtained by RoboPol, a monitoring program of an unbiased sample of gamma-ray bright blazars specially designed for effective detection of such events. A possible connection of polarization swing events with periods of high activity in gamma rays is investigated using the dataset obtained during the first season of operation. It was found that the brightest gamma-ray flares tend to be located closer in time to rotation events, which may be an indication of two separate mechanisms responsible for the rotations. Blazars with detected rotations have significantly larger amplitude and faster variations of polarization angle in optical than blazars without rotations. Our simulations show that the full set of observed rotations is not a likely outcome (probability $\le 1.5 \times 10^{-2}$) of a random walk of the polarization vector simulated by a multicell model. Furthermore, it is highly unlikely ($\sim 5 \times 10^{-5}$) that none of our rotations is physically connected with an increase in gamma-ray activity.Comment: 16 pages, 9 figure

Optical polarization of gamma-ray bright blazars

We report about first results of the RoboPol project. RoboPol is a large-sample, high-cadence, polarimetric monitoring program of blazars in optical wavelengths, using a camera specifically constructed for this project, mounted at the University of Crete's Skinakas Observatory 1.3 m telescope. The analysis of RoboPol data is conducted in conjunction with Fermi LAT gamma-ray data, and multifrequency radio data from the OVRO (Caltech), F-GAMMA (MPIfR), and Torun (NCU) monitoring programs. Using carefully selected samples of gamma-ray bright and weak blazars we investigate a connection between their optical polarization behaviour and variability properties in gamma. We examine a relationship of gamma flares with polarization angle rotations relying on robust statistical criteria. We analyse also the optical polarization variability itself in order to establish some restrictions on physical models of blazars jets

RoboPol: a four-channel optical imaging polarimeter

We present the design and performance of RoboPol, a four-channel optical polarimeter operating at the Skinakas Observatory in Crete, Greece. RoboPol is capable of measuring both relative linear Stokes parameters q and u (and the total intensity I) in one sky exposure. Though primarily used to measure the polarization of point sources in the R band, the instrument features additional filters (B, V, and I), enabling multiwavelength imaging polarimetry over a large field of view (13.6' x 13.6'). We demonstrate the accuracy and stability of the instrument throughout its 5 yr of operation. Best performance is achieved within the central region of the field of view and in the R band. For such measurements the systematic uncertainty is below 0.1 per cent in fractional linear polarization, p (0.05 per cent maximum likelihood). Throughout all observing seasons the instrumental polarization varies within 0.1 per cent in p and within similar to 1 degrees in polarization angle

Dynamics on the Attractor for the Complex Ginzburg-Landau Equation

. We present a numerical study of the large-time asymptotic behavior of solutions to the one-dimensional complex Ginzburg-Landau equation with periodic boundary conditions. Our parameters belong to the Benjamin-Feir unstable region. Our solutions start near a pure-mode rotating wave that is stable under sideband perturbations for the Reynolds number R ranging over an interval (R sub ; R sup ). We find sub- and super-critical bifurcations from this stable rotating wave to a stable 2-torus as the parameter R is decreased or increased past the critical value R sub or R sup . As R ? R sup further increases, we observe a variety of dynamical phenomena, such as a local attractor consisting of three unstable manifolds of periodic orbits or 2-tori cyclically connected by manifolds of connection orbits. We compare our numerical simulations to both rigorous mathematical results and experimental observations for binary fluid mixtures. KEY WORDS. Periodic orbit; 2- and 3-tori; stability; local at..

Chiral Ag(i) and Pt(ii) complexes of ditopic NHC ligands: synthesis, structural and spectroscopic properties

The butyl and isopropyl derivatives (4I, 5Br) of chiral pool derived bis-imidazolium dehydrohexitol salts have been prepared. The ditopic N-heterocyclic carbenes 4 and 5 form dinuclear Ag(I) and Pt(II) complexes. All compounds were fully characterised by multinuclear NMR spectroscopy. The bis-imidazolium salt 4I and platinum complexes cis-[Pt-2(mu-2)(dmso)(2)Cl-4] and cis-[Pt-2(mu-4)(dmso)(2)Cl-4] were characterised by X-ray crystallography. In the case of the Pt(II) complexes, the carbene ring is positioned in a sterically preferred orientation, approximately perpendicular to the platinum coordination plane. The H-1, C-13, N-15 and Pt-195 NMR spectra of the platinum complexes show the presence of rotamers due to hindered rotation about the carbene-metal bond