Theoretical study of α-CD based [3] pseudorotaxanes: the role played by threadlike polymer on the stability of Cyclodextrin dimers

cyclodextrins (cds) and polymeric chains have attracted considerable attention, being addressed in the literature as novel molecular assembly. the so-called "molecular necklace" synthesized by the inclusion of a polymeric chain inside cds cavity has been employed in the formulation of molecular wires and nanotubes. in this paper we applied our previous reported mixed basis set approach in order to investigate theoretically the α-cd inclusion complexes formed by two cd units and an oligo(ethylene glycol) (oeg). in attempt to analyze the role played by the oeg in the formation of pseudo-rotaxane in gas-phase, dft calculations were performed for six possible dimer associations of cds, named head-to-head (hh), tail-to-tail (tt) and head-to-tail (ht) with or without an oeg threadlike molecule included in the cavity formed by the α-cd dimer. the comparison between relative energies of empty (hh, tt and ht) and filled associations (hh-oeg, tt-oeg and ht-oeg) shows that the oeg chain does not interfere significantly in the relative stabilization energies of the supramolecular systems, therefore the relative arrangements of cds in the necklace structures should be primarily driven by interactions between cyclodextrin units.