DARSTELLUNG UND NMR-SPEKTROSKOPISCHE UNTERSUCHUNGEN DER 2-FLUOR-2,2-DIPHENYL-2,3-DIHYDRO-1,3,2λ5-BENZOXAZAPHOSPHOLE

Abstract

Pentakoordinierte Phosphorverbindungen vom Typ der 2.3-Dihydro-1.3.2-benzoxazaphosphole entstehen bei der Umsetzung von 2-Amino-phenolen oder N-Äthyl-2-hydroxy-anilinen mit Diphenyl-trifluorphosphoran unter Verwendung von Triäthylamin als Fluorwasserstoff-Akzeptor. Die Synthese einer großen Anzahl verschieden substituierter Spezies zeigt die Allgemeingültigkeit dieses Verfahrens. Die isolierbaren Substanzen werden durch NMR-Spektren (¹H, ³¹P, ¹⁹F) und die üblichen analytischen Methoden charakterisiert. Die Markierung einer Verbindung mit ¹⁵N trägt wesentlich zur Struktursicherung bei. Bei den 3-H-2-Fluor-2.2-diphenyl-1.3.2-benzoxazaphospholen wurde ein bemerkenswerter Zusammenhang zwischen P–F-Kopplungskonstante und dem F-shift aufgefunden, der eine lineare Korrelation dieser beiden Größen erkennen läßt.

Pentacoordinated phosphorus compounds of the type of 2,3-dihydro-1,3,2-benzoxazaphospholes originate from reaction of 2-aminophenol or N-ethyl-2-hydroxyaniline with diphenyl-trifluorophosphorane using triethylamine as an HF-acceptor. The described synthesis of a great number of differently substituted species indicates the wide field of application. The substances are characterized by nmr spectroscopy (¹H, ³¹P, ¹⁹F) and the usual analytical methods. By marking one compound with ¹⁵N the structure assignment is proved. Remarkably, the compounds of the type 3-H-2-fluoro-2,2-diphenyl-1,3,2-benzoxazaphospholes exhibit a nearly linear correlation between the P–F-coupling constants and the F-chemical shift.     

Terahertz spectroscopy of AuFe spin glasses

The electrodynamic response of spin glasses (in the form of thin AuFe films) in the terahertz frequency range has been studied using backward-wave oscillator (BWO) spectroscopy (10–40 cm^?1) and optical ellipsometry (5000–33000 cm^?1) techniques at temperatures from 5 to 295 K. The room-temperature dynamic conductivity spectra of AuFe films are typical of metals and can be described within the framework of the Drude theory of conduction by free charge carriers. Changes in the microscopic parameters of charge carriers in AuFe films with increasing iron content, which are related to additional scattering of carriers on the impurity magnetic moments, have been studied on the quantitative level, including the carrier relaxation frequency and characteristic time, plasma frequency, and conductivity. It is established that the spin-glass phase at a temperature of ～5 K exhibits dispersion of the conductivity in the frequency range 10–40 cm^?1, which can be related to the appearance of a mobility gap in the subsystem of free electrons involved in the RKKY interaction between magnetic centers (Fe atoms).     

Magnetic susceptibility, heat capacity, and optical conductivity of LiPc and LiPcI

The magnetic susceptibility, using dc and electron spin resonance (ESR) methods, the specific heat, and the infrared properties of the one-dimensional molecular semiconductors lithium phthalocyanine (LiPc) and the iodinated compound LiPcI have been investigated for temperatures K. LiPc has a half-filled conduction band and is expected to be an organic metal. However, due to the strong Coulomb repulsion the system is a one-dimensional Mott-Hubbard insulator with a Hubbard gap of 0.75 eV as inferred from optical measurements. The localized electrons along the molecular stacks behave like a S = 1/2 antiferromagnetic spin chain. The spin susceptibility, as determined by ESR experiments, and the magnetic contribution to the heat capacity show a Bonner-Fisher type of behavior with an exchange constant K. LiPcI is an intrinsic narrow-gap semiconductor with an optical gap of 0.43 eV. In ESR experiments it is silent, indicating that all the unpaired electrons have been removed from the macrocycle via doping with iodine. Received: 16 June 1998 / Accepted: 14 July 1998     

Limits on the high-energy gamma and neutrino fluxes from the SGR 1806-20 giant flare of 27 December 2004 with the AMANDA-II detector

On 27 December 2004, a giant gamma flare from the Soft Gamma-Ray Repeater 1806-20 saturated many satellite gamma-ray detectors, being the brightest transient event ever observed in the Galaxy. AMANDA-II was used to search for down-going muons indicative of high-energy gammas and/or neutrinos from this object. The data revealed no significant signal, so upper limits (at 90% C.L.) on the normalization constant were set: 0.05(0.5) TeV-1 m;{-2} s;{-1} for gamma=-1.47 (-2) in the gamma flux and 0.4(6.1) TeV-1 m;{-2} s;{-1} for gamma=-1.47 (-2) in the high-energy neutrino flux.     

A Rapid Method for Determination of Changes in Shape of Comminuted Particles Using a Laser Diffractometer

The size distributions of carefully screened √2 size fractions of ground materials were determined using a Microtrac laser diffractometer. The size distributions were fitted to the empirical function P(x) = 1/[1 + (x₅₀/x)^λ] where P(x) is cumulative mass fraction less than Microtrac size, x. The standard deviation of λ for a 50 second test time was approximately 0.5, so that seventeen test times give a mean with an estimated error within ± 0.25 (95% confidence level). Values of λ were 5.44, 4.82, 4.40 for a coal ground under different conditions, indicating statistically different shape distributions; the average value for mica was 2.91 owing to the high aspect ratio of the particles. The ratio of x₅₀ to the geometric mean sieve size was 1.2 for the coal and 0.70 for mica.     

Phase diagram of neutron star quark matter in nonlocal chiral models

We analyze the phase diagram of two-flavor quark matter under neutron star constraints for a nonlocal covariant quark model within the mean-field approximation. Applications to cold compact stars are discussed.     

Electromagnetic response of static and fluctuating stripes in cuprate superconductors

Using infrared spectroscopy, we found that changes in the in-plane charge dynamics attributable to static stripe order in La(1.275)Nd(0.6)Sr(0.125)CuO(4) or superconductivity in La(1.875)Sr(0.125)CuO(4) are confined to energies smaller than 100 cm(-1). An absorption peak in the low- omega conductivity of the Nd-doped compound is suggestive of localization effects due to the reduced dimensionality of static charge stripes. Neither superconductivity nor static stripe ordering has a noticeable effect on the depression of the scattering rate at omega<1000 cm(-1) characteristic of the pseudogap state in other classes of moderately doped cuprates.     

Radiative decays of mesons in the NJL model

We revisit the theoretical predictions for anomalous radiative decays of pseudoscalar and vector mesons. Our analysis is performed in the framework of the Nambu–Jona–Lasinio model, introducing adequate parameters to account for the breakdown of chiral symmetry. The results are comparable with those obtained in previous approaches. Received: 14 September 2000 / Revised version: 1 March 2001 / Published online: 8 June 2001