A novel samarium(ii) complex bearing a dianionic bis(phenolate) cyclam ligand: synthesis, structure and electron-transfer reactions.

The reaction of the hexadentate dianionic 1,4,8,11-tetraazacyclotetradecane-based bis(phenolate) ligand, (tBu2ArO)2Me2-cyclam(2-), with [SmI2(thf )2] in thf resulted in the formation of the divalent samarium complex [Sm(κ(6)-{(tBu2ArO)2Me2-cyclam})] (1). X-ray diffraction studies revealed that after recrystallization from n-hexane/thf complex 1 has a monomeric structure and does not contain thf molecules coordinated to the Sm(II) center. However, UV-vis and (1)H NMR spectroscopy of 1 evidenced the formation of thf-solvated complexes in neat thf.

The Slow Molecular Mobility in Amorphous Ketoprofen and Ibuprofen.

The slow molecular dynamics in two active pharmaceutical drugs, ketoprofen and ibuprofen, have been studied by differential scanning calorimetry (DSC) and thermally stimulated depolarization currents (TSDC). This study allowed finding the main kinetic features of the fast secondary (γ) relaxation, of the Johari-Goldstein relaxation, and of the main (glass transition) relaxation, in particular their distribution of relaxation times. The fragility index of the two glass formers was determined based on data from DSC and from TSDC.

The segmental and chain relaxation modes in high-cis-polyisoprene as studied by thermally stimulated currents.

The technique of Thermally Stimulated Currents is used to study the slow molecular mobility in a series of poly (1,4-cis-isoprene) samples with different molecular weights, Mw, and low polydispersity. The technique revealed a high resolution power, particularly useful in the study of the lower molecular weight samples where the chain and the segmental relaxations strongly overlap. The dynamic crossover that is reported for the normal mode by varying the molecular weight is clearly revealed by the thermally stimulated depolarization currents results through the temperature location, TMn, of the normal mode peak, the values of the relaxation time at TMn, τ(TMn), and the value of the fragility index of the normal mode, mn.