Significant modification of the I(-)3 Lewis base character in the β-cyclodextrin polyiodide inclusion complex with Co2+ ion: an FT-Raman investigation

The β-cyclodextrin (β-CD) polyiodide inclusion complex (β-CD)(2)·Co(0.5)·I(7)·21H(2)O has been synthesized, characterized and further investigated via FT-Raman spectroscopy in the temperature range of 30-120°C. The experimental results point to the coexistence of I(-)(7) units (I(2)·I(-)(3)·I(2)) that seem not to interact with the Co(2+) ions and I(-)(7) units that display such interactions. The former units exhibit a disorder-order transition of both their I(2) molecules above 60°C due to a symmetric charge-transfer interaction with the central I(-)(3) [I(2)←I(-)(3)→I(2)], whereas in the latter units only one of the two I(2) molecules becomes well-ordered above 30°C. The other I(2) molecule remains disordered presenting no charge-transfer phenomena. The Co(2+) ion induces a considerable asymmetry on the geometry of the I(-)(3) anion and a significant modification of its Lewis base character. Complementary dielectric measurements suggest no important involvement of H···I contacts in the observed modification of the I(-)(3) electron-transfer properties.     

Using clathrate hydrates for gas storage and gas-mixture separations: experimental and computational studies at multiple length scales

ABSTRACT

Clathrate hydrates have characteristic properties that render them attractive for a number of industrial applications. Of particular interest are the following two cases: (i) the incorporation of large amounts of gas molecules into the solid structure has resulted in considering hydrates as possible material for the storage/transportation of energy or environmental gases, and (ii) the selective incorporation of guest molecules into the solid structure has resulted in considering hydrates for gas-mixture separations. For the proper design of such industrial applications, it is essential to know accurately a number of thermodynamic, structural and transport properties. Such properties can either be measured experimentally or calculated at different scales that span the molecular scale-up to the continuum scale. By using clathrate hydrates as a particular case study, we demonstrate that performing studies at multiple length scales can be utilised in order to obtain properties that are essential to process design.