Synthesis, structures, redox and photophysical properties of benzodifuran-functionalised pyrene and anthracene fluorophores

Benzodifuran-functionalised pyrene and anthracene fluorophores 1 and 2 were obtained in reasonable yields. Their single crystal structures, electrochemical, optical absorption, and fluorescence characteristics have been described. They show strong luminescence with high quantum yields of 0.53 for 1 and 0.48 for 2.     

Synthesis and self-assembly of spin-labile and redox-active manganese(III) complexes

New amphiphilic and spin-labile Mn(III) complexes based on dianionic N(4)O(2)-hexadentate sal(2)trien or sal(2)bapen ligands, which contain OC(6)H(13), OC(12)H(25), or OC(18)H(37) alkoxy substituents at different positions of the salicylidene unit were prepared (H(2)sal(2)trien = N,N'-bis(salicylidene)-1,4,7,10-tetraazadecane, H(2)sal(2)bapen = N,N'-bis(salicylidene)-1,5,8,12-tetraazadodecane). According to electrochemical measurements, these complexes undergo two (quasi)reversible redox processes. Temperature-dependent magnetic measurements revealed a high-spin configuration for all sal(2)trien complexes (S = 2) and gradual spin crossover for sal(2)bapen complexes from high to low spin (S = 1). The chain length strongly influences the spin crossover, as C(18)-functionalization stabilizes the low spin state at much higher temperatures than shorter alkyl chains. Moreover, long alkyl chains allow for spontaneous self-assembly of the molecules, which was investigated in single crystals and in Langmuir-films at the air-water interface. Long alkyl chains (C(12) or C(18)) as well as a mutual syn-orientation of these molecular recognition sites were required for the Langmuir monolayers to be stable.     

Plasma-Beam Discharge with a Pipe-like Electron Beam as the Generator of Large Flows of Active Radicals

Investigations on the device with a tube-like electron beam have been carried out. The behaviour of the plasma-beam discharge in active molecular gases at low pressures and at the pressure P = 1 Torr has been studied. The etching of crystalline silicon by active fluorine radicals has been carried out.     

Influence of isomorphous substitution of metal ion on the low-frequency dielectric dispersion in NH2(CH3)2Al1−xCrx(SO4)2⋅6H2O ferroelectrics

This paper is devoted to the study of the influence of metal ion isomorphous substitution on the ferroelastic-ferroelectric phase transition and dispersion caused by the motion of domain walls in dimethylammonium metal sulfate hexahydrate DMAAl_1?xCr_xS ferroelectric crystals (x = 0, 0.065, 0.2). It is shown that such a substitution significantly changes the phase transition temperature and parameters of the dielectric dispersion. These changes are explained in terms of interaction between the metal-hydrate complexes and DMA groups that carry the dipole moment and due to this they are responsible for the phase transitions and motion of the domain walls.     

Exploratory studies on coordination chemistry of a redox-active bridging ligand: synthesis, properties and solid state structures of the complexes

The explorative coordination chemistry of the bridging ligand TTF-PPB is presented. Its strong binding ability to Co(II) and then to Ni(II) or Cu(II) in the presence of hexafluoroacetylacetonate (hfac(-)), forming new mono- and dinuclear complexes 1-3, is described. X-ray crystallographic studies have been conducted in the case of the free ligand TTF-PPB as well as its complexes [Co(TTF-PPB)(hfac)(2)] (1) and [Co(hfac)(2)(μ-TTF-PPB)Ni(hfac)(2)] (2). Each metal ion is bonded to two bidentate hfac(-) anions through their oxygen atoms and two nitrogen atoms of the PPB moiety with a distorted octahedral coordination geometry. Specifically, nitrogen donor atoms of TTF-PPB adopt a cis-coordination but not in the equatorial plane, which is quite rare. Electronic absorption, photoinduced intraligand charge transfer ((1)ILCT), and electrochemical behaviour of 1-3 have been investigated. UV-Vis spectroscopy shows very strong bands in the UV region consistent with ligand centred π-π* transitions and an intense broad band in the visible region corresponding to a spin-allowed π-π* (1)ILCT transition. Upon coordination, the (1)ILCT band is bathochromically shifted by 3100, 6100 and 5900 cm(-1) on going from 1 to 3. The electrochemical studies reveal that all of them undergo two reversible oxidation and one reversible reduction processes, ascribed to the successive oxidations of the TTF moiety and the reduction of the PPB unit, respectively.     

In situ conduction ESR and theoretical studies of graphite intercalation by antimony pentafluoride

The results of an in situ conduction electron spin resonance (CESR) study of the intercalation of SbF₅ molecules into highly oriented pyrolytic graphite are presented. The narrowing (broad-ening) of the CESR signal from intercalated (nonintercalated) parts of the graphite plate during advance of the reaction front into graphite is explained by the nonzero probability of the spin reorientation at collisions of current carriers with the intercalation front and by a decrease (increase) of frequency of these collisions. The assumption was made that the stepwise increase in the intensity of the CESR signal from intercalated parts of the graphite plate during the reaction is due to the presence of an intercalation threshold and periodical impoverishing of the adsorbed layers of the intercalant. The results of calculations conducted within the framework of this model fit the experimental data well. Presented at the 5th Asia-Pasific EPR/ESR Symposium, August 24–27, 2006, Novosibirsk, Russian Federation.     

Effect of carbon on accumulation of deuterium in beryllium irradiated with stationary plasma

Beryllium targets placed in the PLAST beam-plasma discharge facility were irradiated with a flux of stationary deuterium (D) plasma with a deuterium ion energy of 200 eV and plasma flux density of 3 × 10²⁰ m^?2 s^?1 at temperatures of 370 and 670 K. The irradiation doses varied from 5 × 10²¹ to 10²⁴ m^?2. To heat the target and to ionize impurities near its surface the target was irradiated with an electron beam. The deuterium concentration at the target center exceeds its concentration at the periphery by a factor of more than two under all irradiation conditions. The target center was enriched with carbon up to 16–24 at %, as compared to 4–6 at % at the target periphery. The [D]: [Be] atomic concentration ratios at the target center were equal to 0.054 and 0.036 against 0.024 and 0.016 at the periphery at temperatures of 370 and 670 K, respectively. It has been found that these ratios depend on the concentration of carbon atoms which trapped deuterium atoms.