We will report on the kinetics and thermodynamics associated with the electrochemically driven molecular mechanical switching of the bistable [2]rotaxanes A and B in solution, polymer electrolyte gels and molecular-switch tunnel junctions (MSTJs). For all the rotaxanes, an electron-deficient cyclobis(paraquat-p-phenylene) (CBPQT4+) ring component encircles one of two recognition sites within a dumbbell component. The [2]rotaxanes contain tetrathiafulvalene (TTF) / monopyrrolotetrathiafulvalene (MPTTF) / bispyrrolotetrathiafulvalene (BPTTF) and 1,5-dioxynaphthalene (DNP) recognition units. Oxidation of the TTF (MPTTF or BPTTF) unit is accompanied by movement of the CBPQT4+ ring to the DNP site. Reduction back to TTF (MPTTF or BPTTF) is followed by relaxation to the equilibrium distribution of translational isomers. The relaxation kinetics of are strongly environmentally dependent, yet consistent with a single electromechanical-switching mechanism operating in solution, polymer electrolyte gels, and MSTJs. The ground-state equilibrium properties of the bistable [2]rotaxanes A and B were reflective of molecular structure in all environments. These results provide direct evidence for the control by molecular structure of the electronic properties exhibited by the MSTJs. Moreover, the switchable, bistable [2]rotaxane C containing a rigid and linear backbone was constructed. Compared to our previous results, this new rigid bistable [2]rotaxane will enhance the superstructural integrity during the solid-state switching in the cross-bar device as well as switching in self-assembling monolayers. Finally, we have also developed a highly convergent approach to the synthesis of electrochemically switchable mechanically interlocked molecules. The Cu(I)-catalyzed 1,3-cycloaddition of organic azides and alkynes (click chemistry) has been utilized to efficiently prepare [2], [3], and [4]rotaxanes and catenanes, many of which were synthetically inaccessible before the development of this methodology. New methods of incorporating interlocked molecules and polymeric materials into molecular electronic devices using click chemistry will also be discussed.