Investigation of the extraction equilibria in the system hexachloridorhenate(IV)-neotetrazolium chloride-dichloroethane-water

The neotetrazolium hexachloridorhenate(IV) (NTReCl(6)) has been synthesized and its composition checked. The optimum conditions for the extraction of NTReCl(6) with dichloroethane have been established. The recovery factor for one-fold extraction is R = 74%. The distribution constant, K(D), extraction constant, K(ex), and ion-association constant, beta, have been determined. Neotetrazolium chloride was found to be suitable reagent for extraction-spectrophotometric determination of rhenium(IV) ((NTReCl(6)) = 3.42 +/- 0.20 x 10(4)M(-1) cm(-1)).     

Electron phonon systems from weak to strong coupling

Electron and phonon spectra are derived for an electron-phonon system coupled by the Fröhlich interaction. We cover the range from small coupling <1 to large coupling 1 for a commensurate filling of the bare band. The evolution of the Migdal solution into a charge density wave and finally into a regular lattice of small polarons is studied.     

Rossby solitary vortices,on giant planets and in the laboratory

This is a review of laboratory experiments with a layer of shallow water having a free surface and rotating together with a vessel of parabolic form. Such a (rather original) setup has allowed one to create Rossby solitary vortex for the first time. The latter is an anticyclonic Rossby vortex not subjected to dispersive spread owing to its compensation by the nonlinearity of KdV type. By its structural, collisional, and other properties, including clear-cut cyclonic-anticyclonic asymmetry, it may be considered as a physical prototype of the large-scale long-lived anticyclonic Rossby vortices like the Great Red Spot of Jupiter or the Great Dark Spot of Neptune (this remarkable vortex was discovered by the spacecraft Voyager-2 during its farewell to the Solar System) and other vortices dominating in the atmospheres of giant planets and created by the unstable zonal flows. It has been shown that the vortex under study is a long-lived entity provided it satisfies "antitwisting condition," i.e., it has rather large amplitude (at which it rotates more quickly than it propagates and thereby carries the trapped fluid). In this case, it is not subjected to the "twisting" deformation and may be ascribed by the generalized Charney-Obukhov equation for Rossby vortices on shallow water with a free surface. The results of creating the vortex under consideration by the different methods have been compared with the results obtained by other authors in the experiments on shear-flow generation of Rossby vortices.     

Some remarks on coherent structures out of chaos in planetary atmospheres and oceans

In the context of planetary atmospheres and oceans, it is natural to define "coherent structures" as "long-lived," or "solitary," Rossby vortices. These can be described by the generalized Charney-Obukhov equation (in fluid dynamics) or the analogous generalized Hasegawa-Mima equation (in plasma physics). These two equations contain KdV-type nonlinearities which (together with the compensating dispersive spreading) determine the formation of the coherent structures and explain the clear-cut cyclonic/anticyclonic asymmetry observed experimentally in long-lived planetary Rossby vortices. Examples are given of natural vortices which are (and which are not) coherent structures.     

Synthesis, crystal structure, and nonlinear optical behavior of beta-unsubstituted meso-meso E-vinylene-linked porphyrin dimers

[structure: see text] A vinylene-linked porphyrin dimer, with no substituents at the beta-positions, has been synthesized by CuI/CsF promoted Stille coupling. In the crystal structure of this dimer, the C(2)H(2) bridge is twisted by 45 degrees relative to the plane of the porphyrins. The absorption, emission spectra, and electrochemistry reveal substantial porphyrin-porphyrin pi-conjugation. The triplet excited-state absorption spectrum of this dimer makes it suitable for reverse saturable absorption at 710-900 nm.     

Uncertainty of measurement. Twenty years afterwards

The application of the concept "uncertainty" causes considerable difficulties. In this paper an analysis of the intrinsic contradictions of the concept itself and its relationship with the statements of metrology is given with the aim of establishing possible reasons for these difficulties. As a result of this analysis several examples are presented to demonstrate the conflicts of the concept and its several statements in the general fundamental notions of metrology.     

Ultrafast energy-electron transfer cascade in a multichromophoric light-harvesting molecular square

A molecular square with dimensions of about 4 nm, incorporating sixteen pyrene chromophores attached to four ditopic bay-functionalized perylene bisimide chromophores, has been synthesized by coordination to four Pt(II) phosphine corner units and fully characterized via NMR spectroscopy and ESI-FTICR mass spectrometry. Steady-state and time-resolved emission as well as femtosecond transient absorption studies reveal the presence of a highly efficient (>90%) and fast photoinduced energy transfer (k(en) approximately equal to 5.0 x 10(9) s(-1)) from the pyrene to the perylene bisimide chromophores and a very fast and efficient electron transfer (>94%, k(et) approximately equal to 5 x 10(11) up to 43 x 10(11) s(-1)). Spectrotemporal parametrization indicates upper excited-state electron-transfer processes, various energy and electron-transfer pathways, and chromophoric heterogeneity. Temperature-dependent time-resolved emission spectroscopy has shown that the acceptor emission lifetime increases with decreasing temperature from which an electron-transfer barrier is obtained. The extremely fast electron-transfer processes (substantially faster and more efficient than in the free ligand) that are normally only observed in solid materials, together with the closely packed structure of 20 chromophoric units, indicate that we can consider the molecular square as a monodisperse nanoaggregate: a molecularly defined ensemble of chromophores that partly behaves like a solid material.     

Synthesis of thiadiazabicyclane and bis-1,3,5-dithiazinane by cyclothiomethylation of aliphatic diamines with CH2O and H2S

Cyclocondensation of aliphatic diamines with CH₂O and H₂S (1:3:2 ratio, 0 °C) was carried out to give thiadiazabicyclanes and dithiadiazabicyclanes (1:6:4 ratio), which were previously difficult to synthesize. Symmetric α,ω-bis-1,3,5-dithiazinanes were synthesized at 80 °C by this reaction. The stereochemistry of thiadiazabicyclanes was assigned by ¹H and ¹³C NMR spectroscopy and by theoretical DFT calculations, and of bis-dithiazinanes by X-ray diffraction study in the solid state.     

A novel heteropolycyclic system from n-methylquinoxalinium iodide and nitroethane

Reaction of N-methylquinoxalinium iodide with nitroethane results in either the 1:2 diadduct at C-2 and C-3 or the formation of substituted 1,3,6,10-tetraazatetracyclo[7.3.1.0.^2,70^6,13] tridecane derivative.     

Synthesis of macrocycles incorporating azo‐bis(azofurazan) framework

A series of macrocycles containing four furazan rings bonded by three azo bonds 2, 5 and 7 have been synthesized from the common precursor, 3‐amino‐3′‐nitro(azofurazan) 3 . The macrocycles closure is a result of N?N bond formation at oxidative cyclization of corresponding bis(3‐aminofurazan‐4‐yl) precursors. X‐Ray crystal structures of macrocycles 2, 2 ?AcOH, 11 and 13 are reported.