title: Kinetic Study of [2]Pseudorotaxane Formation with an Asymmetrical Thread.
abstract: Kinetic and thermodynamic studies on cyclodextrin (CD)-based [2]pseudorotaxane formation have been carried out by a combination of NMR and calorimetric techniques using bolaform surfactants as axles. Experimental evidence of the formation of an external complex between the trimethylammonium head groups of the axle and the external hydrogen atoms of α-cyclodextrin (α-CD) is reported. Inclusion of this external complex in the reaction pathway allows us to explain the kinetic behavior as well as the nonlinear dependence of the observed rate constant on CD concentrations. The equilibrium constant for [2]pseudorotaxane formation is strongly affected by the spacer length of the axle. This effect is a consequence of increasing rotaxane stability because the threading rate constant is almost independent of the spacer length, but dethreading strongly decreases on increasing the axle size. Using a nonsymmetrical axle with tripropyl and trimethylammonium cations precludes CD threading by the large head side. CDs will thread this asymmetrical bolaform by both their wide and narrow sides, yielding two isomeric [2]pseudorotaxanes. Threading by the wide side of the CD is 60% more favorable than that by the narrow one, but dethreading rate constants are the same for both isomers.
authors.affiliation: Departamento de Química Física, Centro de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS), Facultade de Química, Universidade de Santiago de Compostela , 15782 Santiago, Spain.
authors.forename: Miguel
authors.initials: M
authors.lastname: Quiroga
authors.affiliation: Departamento de Química Física, Centro de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS), Facultade de Química, Universidade de Santiago de Compostela , 15782 Santiago, Spain.
authors.forename: Mercedes
authors.initials: M
authors.lastname: Parajó
authors.affiliation: Departamento de Química Física, Centro de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS), Facultade de Química, Universidade de Santiago de Compostela , 15782 Santiago, Spain.
authors.forename: Pedro
authors.initials: P
authors.lastname: Rodríguez-Dafonte
authors.affiliation: Departamento de Química Física, Centro de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS), Facultade de Química, Universidade de Santiago de Compostela , 15782 Santiago, Spain.
authors.forename: Luis
authors.initials: L
authors.lastname: García-Río