Nanomachines of the future will require molecular-scale motors that can perform work and collectively induce controlled motion of much larger objects. We have designed a synthetic, light-driven molecular motor that is embedded in a liquid-crystal film and can rotate objects placed on the film that exceed the size of the motor molecule by a factor of 10,000. The changes in shape of the motor during the rotary steps cause a remarkable rotational reorganization of the liquid-crystal film and its surface relief, which ultimately causes the rotation of submillimetre-sized particles on the film.
Molecules capable of mimicking the function of a wide range of mechanical devices have been fabricated, with motors that can induce mechanical movement attracting particular attention. Such molecular motors convert light or chemical energy into directional rotary or linear motion, and are usually prepared and operated in solution. But if they are to be used as nanomachines that can do useful work, it seems essential to construct systems that can function on a surface, like a recently reported linear artificial muscle. Surface-mounted rotors have been realized and limited directionality in their motion predicted. Here we demonstrate that a light-driven molecular motor capable of repetitive unidirectional rotation can be mounted on the surface of gold nanoparticles. The motor design uses a chiral helical alkene with an upper half that serves as a propeller and is connected through a carbon-carbon double bond (the rotation axis) to a lower half that serves as a stator. The stator carries two thiol-functionalized 'legs', which then bind the entire motor molecule to a gold surface. NMR spectroscopy reveals that two photo-induced cis-trans isomerizations of the central double bond, each followed by a thermal helix inversion to prevent reverse rotation, induce a full and unidirectional 360 degrees rotation of the propeller with respect to the surface-mounted lower half of the system.
Structural modification of unidirectional light-driven rotary molecular motors in which the naphthalene moieties are exchanged for substituted phenyl moieties are reported. This redesign provides an additional tool to control the speed of the motors, and should enable the design and synthesis of more complex systems.
With the long-term goal of producing nanometer-scale machines, we describe here the unidirectional rotary motion of a synthetic molecular structure fueled by chemical conversions. The basis of the rotation is the movement of a phenyl rotor relative to a naphthyl stator about a single bond axle. The sense of rotation is governed by the choice of chemical reagents that power the motor through four chemically distinct stations. Within the stations, the rotor is held in place by structural features that limit the extent of the rotor's Brownian motion relative to the stator.
One of the key challenges in taking light‐driven unidirectional rotary motors from discovery to application is to increase the rate of rotation. Herein, we review our ongoing efforts to address this issue by meticulous improvement to the molecular design. To accelerate the rotary cycle, we have focused primarily on the rate‐limiting thermal isomerization step. This has been a fascinating and formidable objective, given that the first system we reported had a half‐life of over one week at room temperature! Our research has ultimately led to the construction of a unidirectional rotary molecular motor with a cycle 108 times faster than the original; that is, it can in principle function at 44 rotations per second.
The fully reversible three-state blue/red/off emission from photo-/electrochromic substituted bis-thiaxanthylidenes is reported. The blue luminescence of the most stable (anti-folded) conformer of dimethyl- and dimethoxy-bis-thiaxanthylidene can be switched off by photochemical conversion to the meta-stable (syn-folded) conformer and switched on again by thermal reversion to the anti-folded state. The red luminescence of the bis-thiaxanthylium dication can be switched on by oxidation at approximately 1.0 and 1.2 V vs SCE of the syn- and anti-folded conformers respectively and switched off or to blue by reduction at approximately 0.35 V vs SCE.
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