Europium metallic systems

Eu—N system. — EuN was prepared [240] by direct combination of europium metal and nitrogen at 800° C. Keemm and Winkelmann s preparation [241] involved heating (700°) a mixture of finely divided europium and KC1 (1 3) in a stream of NH3. EuN, like SmN and YbN possesses the NaCl type structure. The lattice constant of EuN is a = 5.014 A according to Klemm and Winkelmann [241], and a = 5.007 0.004 A according to Eick et al [240]. However, the preparation of Eick et al. contained some impurity, possibly as oxide. 

Eu—G system.—The black dicarbide, EuC2, was prepared by GEBELTand Eick [231] by the reaction of europium metal with graphite (1 2 ratio) in a steel bomb at about 1050° G. The compound has a body-centered tetragonal structure with the lattice parameters a = 4.045 and c 6.645 A. The lattice constants compare reasonably well with SrC2 (a = 4.11, c = 6.68 A). 

A systematic study of the Eu/Yb and Eu/Ba alloys has been made [52, 53]. In the ytterbium system, the Curie temperature falls from 90 to 5 K and the saturation field also falls from 265 to 160 kG as the ytterbium content increases from 0 to 92 at. %. The relationships are linear apart from a discontinuity at 50 at. % where there is a phase change. Similarly for barium the Curie temperature falls from 90 to 40 K and the field from 265 to 206 kG as the barium content rises to 50 at. %. However, the chemical isomer shift is not significantly altered. The sign of the magnetic field is known to be negative from neutron diffraction data. Calculations suggest that a contribution of —340 kG to the field in europium metal arises from core polarisation, that +190 kG comes from conduction-electron polarisation by the atoms own 4/-electrons, and that —115 kG comes from conduction-electron polarisation, overlap, and covalency effects from neighbouring atoms. 

Recent studies of in EuRu2Ge2 (Nowik Felner, 1984) where the europium ion is divalent and is exposed to the largest electric field gradient ever observed in any rare earth metallic system, yield the temperature dependence of f and fj shown in Figure 6.6. 

The last chapter (134) in this volume is an extensive review by Colinet and Pasturel of the thermodynamic properties of landianide and actinide metallic systems. In addition to compiling useful theiTnodynamic data, such as enthalpies, entropies, and free eneigies of formation and of mixing, the authors have made an extensive comparative analysis of the thermodynamic behavior of the rare earths and actinides when alloyed with metallic elements. They note that when alloyed with non-transition metals, the enthalpies of formation of uranium alloys are less negative than those of the rare earths while those of thorium and plutonium are about the same as the latter. For transition metal alloys the formation enthalpies of thorium and uranium are more negative than diose of the rare earths and plutonium (the latter two are about the same). The anomalous behaviors of cerium, europium and ytterbium in various compounds and alloys are also discussed along with the effect of valence state changes found in uranium and plutonium alloys. 

Similar to chemical vapor deposition, reactants or precursors for chemical vapor synthesis are volatile metal-organics, carbonyls, hydrides, chlorides, etc. delivered to the hot-wall reactor as a vapor. A typical laboratory reactor consists of a precursor delivery system, a reaction zone, a particle collector, and a pumping system. Modification of the precursor delivery system and the reaction zone allows synthesis of pure oxide, doped oxide, or multi-component nanoparticles. For example, copper nanoparticles can be prepared from copper acetylacetone complexes [70], while europium doped yttiria can be obtained from their organometallic precursors [71]. 

For those complexes where the chromophore is not coordinated to the metal center directly, the orientation of the chromophore is important to ensure efficient energy transfer. The series of ligands L29-L32 were investigated for correlations between structural parameters found in the solid state (see, for example, Fig. 12) and solution (by NMR spectroscopy) and photophysical properties (69,70). It was found that both chromophore-metal separation and the angle of orientation have a direct influence on the quantum yield of the europium complexes. For example, the difference in quantum yield between [Eu(L29)]3+ and [Eu(L30)]3+ (0.06 and 0.02, respectively) cannot be attributed solely to the chromophore-metal separation, so may also depend on the better orientation of the chromophore in the L29 system as measured by the angle a between the metal center, the amide nitrogen atom, and the center of the phenyl ring. 

This chapter commences with a review of a limited number of ternary hydride systems that have two common features. First, at least one of the two metal constituents is an alkali or alkaline earth element which independently forms a binary hydride with a metal hydrogen bond that is characterized as saline or ionic. The second metal, for the most part, is near the end of the d-electron series and with the exception of palladium, is not known to form binary hydrides that are stable at room temperature. This review stems from our own more specific interest in preparing and characterizing ternary hydrides where one of the metals is europium or ytterbium and the other is a rarer platinum metal. The similarity between the crystal chemistry of these di-valent rare earths and Ca2+ and Sr2+ is well known so that in our systems, europium and ytterbium in their di-valent oxidation states are viewed as pseudoalkaline earth elements. 

Interactions of ofloxacin and levofloxacin with Al3+, Fe3+, and Mg2+ ions were investigated by capillary zone electrophoresis (07CHR489). A fluorescence enhancement phenomenon in the europium-ofloxacin-sodium dodecyl benzenesulfonate fluorescence system was observed when Gd3+ was added (07JFL105). A quantitative relation was found between the relative fluorescences of Zr, Mo, and V chelates of ofloxacin and the ionization of the carboxylic group and the calculated stability constants of the formed chelates (06MI34). Factors that significantly influence the stability of ofloxacin- and levofloxacin-metal (Al3+, Fe3+, Cu2+,... 

A derivative of the (bpy.bpy.bpy) cryptand, obtained by modifying one of the chains, Lbpy, forms a di-protonated cryptate with EuCb in water at acidic pH, [EuCl3(H2Lbpy)]2+ in which the metal ion is coordinated to the four bipyridyl and two bridgehead nitrogen atoms, and to the three chlorine ions (Fig. 4.25). The polyamine chain is not involved in the metal ion coordination, due to the binding of the two acidic protons within this triamine subunit. In solution, when chlorides are replaced by perchlorate ions, two water molecules coordinate onto the Eu(III) ion at low pH and one at neutral pH, a pH at which de-protonation of the amine chain occurs, allowing it to coordinate to the metal ion. As a result, the intensity of the luminescence emitted by Eu(III) is pH dependent since water molecules deactivate the metal ion in a non-radiative way. Henceforth, this system can be used as a pH sensor. Several other europium cryptates have been developed as luminescent labels for microscopy. 

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