Langmuir and Langmuir−Blodgett Films of Amphiphilic Bistable Rotaxanes

A series of amphiphilic bistable [2]rotaxanes--in which a ring-shaped component, the tetracationic cyclophane, cyclobis(paraquat-p-phenylene), has been assembled around two recognition sites, a tetrathia-fulvalene (TTF) unit and a 1,5-dioxynaphthalene (DNP) ring system, situated apart at different strategic locations within the central polyether section of an amphiphilic dumbbell component that is terminated by a hydrophobic tetraarylmethane-based stopper (near the TTF unit) at one end and by a hydrophilic tetraarylmethane-based stopper (near the DNP ring system) at the other end--has been designed and synthesized. The effects of systematic changes in the constitutions of the three ethylene glycol tails (diethylene or tetraethylene glycol) and end groups (hydroxyl or methoxyl functions) attached to the hydrophilic stoppers on Langmuir film balance and surface rheology experiments at 20 degreesC were examined to determine the monolayer stabilities and co-conformations of the [2] rotaxanes and their free dumbbell counterparts. These experiments allow us to propose a model for the rotaxane's structures at different surface pressures. All the [2]rotaxanes form stable Langmuir films. These films typically pass from a liquid-expanded region to a liquid-condensed region. The transition between the two regions was either directly observed or ascertained using film stability experiments. Film balance and surface rheology experiments showed that the addition of the tetracationic cyclophane component and hydroxyl end groups markedly increased the stabilities and viscoelasticity of the films.