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Keywords:

  • electrostatic barriers;
  • host–guest chemistry;
  • hydrophobic interactions;
  • rotaxanes;
  • spectrophotometric techniques;
  • template synthesis

Abstract

The ability to control the kinetic barriers governing the relative motions of the components in mechanically interlocked molecules is important for future applications of these compounds in molecular electronic devices. In this Full Paper, we demonstrate that bipyridinium (BIPY2+) dications fulfill the role as effective electrostatic barriers for controlling the shuttling and threading behavior for rotaxanes and pseudorotaxanes in aqueous environments. A degenerate [2]rotaxane, composed of two 1,5-dioxynaphthalene (DNP) units flanking a central BIPY2+ unit in the dumbbell component and encircled by the cyclobis(paraquat-p-phenylene) (CBPQT4+) tetracationic cyclophane, has been synthesized employing a threading-followed-by-stoppering approach. Variable-temperature 1H NMR spectroscopy reveals that the barrier to shuttling of the CBPQT4+ ring over the central BIPY2+ unit is in excess of 17 kcal mol−1 at 343 K. Further information about the nature of the BIPY2+ unit as an electrostatic barrier was gleaned from related supramolecular systems, utilizing two threads composed of either two DNP units flanking a central BIPY2+ moiety or a central DNP unit flanked by a BIPY2+ moiety. The threading and dethreading processes of the CBPQT4+ ring with these compounds, which were investigated by spectrophotometric techniques, reveal that the BIPY2+ unit is responsible for affecting both the thermodynamics and kinetics of pseudorotaxane formation by means of an intramolecular self-folding (through donor–acceptor interactions with the DNP unit), in addition to Coulombic repulsion. In particular, the free energy barrier to threading (Δequation image) of the CBPQT4+ for the case of the thread composed of a DNP flanked by two BIPY2+ units was found to be as high as 21.7 kcal mol−1 at room temperature. These results demonstrate that we can effectively employ the BIPY2+ unit to serve as electrostatic barriers in water in order to gain control over the motions of the CBPQT4+ ring in both mechanically interlocked and supramolecular systems.