Formation of a rotaxane from the end-capping process of a pseudorotaxane. Effects of the solvent

The Journal of Physical Chemistry. B
R JimenezP Lopez-Cornejo

Abstract

The effects that the solvent exerts on the end-capping process of a pseudorotaxane formed by the [Ru(NH 3) 5(4,4'-bpy)]2+ complex and beta-cyclodextrin were studied. In this process the 4,4'-bpy ligand acts as rigid axle and the cyclodextrin as ring or macrocycle. The stopper used was the [Fe(CN) 5 H2O]3(-) complex. The solvents used were mixtures of ethyleneglycol-water and tert-butyl alcohol-water. Results showed similar, although strange, behavior in both media studied. Thus, a decrease of the observed rate constant was obtained when the concentration of cyclodextrin increases for all the media studied. However, at fixed cyclodextrin concentrations, an increase of k obs was obtained when small quantities of the cosolvent were added to the medium and, further, a decrease of k obs for the higher quantities of the organic solvents. This strange behavior could be explained by taking into account electrostatic and specific solvent (solvent-solvent and solvent-solute) effects.

References

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Citations

Dec 24, 2009·Journal of the American Chemical Society·Barbara KirchnerChristoph A Schalley
Mar 26, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·M Lopez-LopezP Lopez-Cornejo
Aug 14, 2010·The Journal of Physical Chemistry. B·Andrés Guerrero-MartínezGloria Tardajos

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