Beyond switches: Rotaxane- and catenane-based synthetic molecular motors*

Abstract: Nature uses molecular motors and machines in virtually every significant biologi-cal process, but learning how to design and assemble simpler artificial structures that func-tion through controlled molecular-level motion is a major challenge for contemporary phys-ical science. The established engineering principles of the macroscopic world can offer little more than inspiration to the molecular engineer who creates devices for an environment where everything is constantly moving and being buffeted by other atoms and molecules. Rather, experimental designs for working molecular machines must follow principles derived from chemical kinetics, thermodynamics, and nonequilibrium statistical physics. The re-markable characteristics of interlocked molecules make them particularly useful for investi-gating the control of motion at the molecular level. Yet, the vast majority of synthetic mo-lecular machines studied to date are simple two-state switches. Here we outline recent developments from our laboratory that demonstrate more complex molecular machine func-tions. This new generation of synthetic molecular machines can move continuously and pro-gressively away from equilibrium, and they may be considered true prototypical molecular motors. The examples discussed exemplify two, fundamentally different, “Brownian ratchet” mechanisms previously developed in theoretical statistical physics and realized experimen-tally in molecular-level devices for the first time in these systems