Molten salt synthesis of a mixed-valent lanthanide(III/IV) oxychloride with an unprecedented Sillen X(2)(4) structure: Ce1.3Nd0.7O3Cl.

A new cerium neodymium oxychloride, Ce1.3Nd0.7O3Cl, has been synthesized by precipitation in a LiCl­CaCl2 molten salt by humid argon sparging. Chemical and structure characterization have been undertaken by powder X-ray diffraction, scanning electron microscopy, high-temperature X-ray diffraction, thermogravimetric analysis, and X-ray photoelectron scattering. This oxychloride crystallizes in space group P4/nmm, a = 3.9848(3) Å and c = 12.467(2) Å, in a new Sillen-type phase represented by the symbol X(2)(4) where "quadruple" fluorite-type layers [M4O6], containing Ce(IV) in "inner" sublayers and both CeIII and NdIII in "outer" sublayers, alternate with double-halide ion sheets. The structure is also described as a stacking of LnOCl and fluorite-type blocks and constitutes the term n = 2 of a possible series (MO2)n(NdOCl)2.

Synthesis, Structural Analysis, and Properties of N-Alkylglucosyl(meth)acrylamides: New Reactive Sugar Surfactants.

New reactive-surfactants, N-alkylglucosylacrylamides and N-alkylglucosylmethacrylamides, are easily prepared in two steps from glucose without protection. The complete structural analysis of these compounds by 1D and 2D NMR spectroscopy shows the existence of a rotational isomerism that is strongly dependent on the steric hindrance of the carbonyl substituent: whatever the alkyl chain length, both endo and exo rotamers are observed for N-alkylglucosylacrylamides 1 while the endo rotamer is the sole species observed in the case of N-alkylglucosylmethacrylamides 2. For acrylamido derivatives 1, the exo-endo equilibrium is solvent-dependent: the endo isomer is favored in polar nonaqueous solvents (endo-exo isomeric ratio R = 70/30) while the equilibrium is shifted toward the exo rotamer in protic acidic medium (R = 50/50 in water and 80/20 in acidic medium). An intramolecular hydrogen bond is assumed to be responsible for the increased stability of the endo rotamer. Furthermore, for tetra-O-acetylated derivatives the exo rotamer becomes favored in aprotic solvents. Surface tension measurements demonstrate that N-octyl- to -tetradecyl-substituted compounds 1 and 2 are surfactants with critical micelle concentrations ranging from 1.2 x 10(-2) to 1.7 x 10(-5) mol/L.