title: Two-dimensional vibrational spectroscopy of rotaxane-based molecular machines.
abstract: It has recently become possible to synthesize mechanical devices the size of a single molecule. Although it is tempting to regard such molecular machines as nanoscale versions of their macroscopic analogs, many notions from macroscopic mechanics no longer apply at a molecular level. For instance, the concept of viscous friction is meaningless for a molecular machine because the size of the solvent molecules that cause the friction is comparable to that of the machine itself. Furthermore, in many cases, the interactions between a molecular machine and its surroundings are comparable to the force driving the machine. As a result, a certain amount of intrinsic randomness exists in the motion of molecular machines, and the details of their mechanics are largely unknown. For a detailed understanding of the mechanical behavior of molecular machines, experiments that probe their motion on an ultrafast time scale, such as two-dimensional (2D) vibrational spectroscopy, are essential. This method uses coupling between vibrational modes in a molecule to investigate the molecular conformation. The coupling shows up as off-diagonal peaks in a 2D graph of the vibrational response of the molecule, analogous to the spin coupling observed in multidimensional NMR spectroscopy. Both spin coupling and vibrational coupling are sensitive probes of the molecular conformation, but 2D vibrational spectroscopy shows orders of magnitude better time resolution than NMR. In this Account, we use 2D vibrational spectroscopy to study molecular machines based on rotaxanes. These devices consist of a linear thread and a macrocycle that is noncovalently locked onto the thread. In the rotaxanes we study, the macrocycle and the thread both contain CO and NH groups. By determining the coupling between the stretching modes of these goups from the cross peaks in the 2D spectrum, we directly and quantitatively probe the relative position and orientation of the macrocycle and the thread for both a small model rotaxane and a rotaxane-based molecular shuttle. Our results demonstrate the feasibility of using time-resolved 2D-IR experiments to measure externally triggered structural changes of molecular devices with subpicosecond time resolution. We can observe each of the elementary events that underlie the mechanical motion separately. With this ability to investigate the nature of the mechanical motions at the molecular level and with unprecedented time resolution, we expect that 2D-IR spectroscopy on molecular machines will lead to new insights into their function.
authors: Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands.
authors: Pavol
authors: P
authors: Bodis
authors: Matthijs R
authors: MR
authors: Panman
authors: Bert H
authors: BH
authors: Bakker
authors: Aurelio
authors: A
authors: Mateo-Alonso
authors: Maurizio
authors: M
authors: Prato
authors: Wybren Jan
authors: WJ
authors: Buma
authors: Albert M
authors: AM
authors: Brouwer
authors: Euan R
authors: ER
authors: Kay
authors: David A
authors: DA
authors: Leigh
authors: Sander
authors: S
authors: Woutersen
mesh_terms: D000042:Absorption; D003116:Color; D008958:Models, Molecular; D008968:Molecular Conformation; D043862:Rotaxanes / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D014732:Vibration
chemical_list: D043862:Rotaxanes