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Prototypes of Molecular Gears with an Organometallic Piano-Stool Architecture
Abstract
In the field of Molecular Machines, molecular gears have mainly been synthesized to be studied in solution. Then, the cogwheel subunits are restricted to be only arranged in an intramolecular manner. In the last years, the possibility to arrange a train of gears at the single molecular level and observe the propagation of a rotation motion from one molecule to its neighbor using Scanning Tunneling Microscopy (STM) opened new perspectives with the opportunity to have intermolecular arrangements on surfaces. In this chapter, we describe the research background of single molecular gears and our strategy using organometallic piano-stool complexes to anchor such gears on surfaces. Our molecules incorporate two subunits linked together through a ruthenium center acting as a ball bearing. The lower part is the anchoring tripodal ligand and the upper part the cogwheel. Various functionalities have been explored to behave as teeth, ranging from mono-dimensional phenyl rings to bi-dimensional porphyrin fragments.
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Synthetic molecular machines designed to operate on materials surfaces can convert energy into motion and they may be useful to incorporate into solid state devices. Here, we develop and characterize a multi-component molecular propeller that enables unidirectional rotations on a material surface when energized. Our propeller is composed of a rotator with three molecular blades linked via a ruthenium atom to a ratchet-shaped molecular gear. Upon adsorption on a gold crystal surface, the two dimensional nature of the surface breaks the symmetry and left or right tilting of the molecular gear-teeth induces chirality. The molecular gear dictates the rotational direction of the propellers and step-wise rotations can be induced by applying an electric field or using inelastic tunneling electrons from a scanning tunneling microscope tip. By means of scanning tunneling microscope manipulation and imaging, the rotation steps of individual molecular propellers are directly visualized, which confirms the unidirectional rotations of both left and right handed molecular propellers into clockwise and anticlockwise directions respectively.
Nature Communications volume 10, Article number: 3742 (2019)
The first race involving molecular 'cars' stimulated technical advances in scanning tunnelling microscopy and provided insights in surface science and synthetic chemistry - it also attracted wide interest from the public. © 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
Metal ions can serve as a centre of molecular motions due to their coordination geometry, reversible bonding nature and external stimuli responsiveness. Such essential features of metal ions have been utilized for metal-mediated molecular machines with the ability to motion switch via metallation/demetallation or coordination number variation at the metal centre; however, motion switching based on the change in coordination geometry remain largely unexplored. Herein, we report a PtII-centred molecular gear that demonstrates control of rotor engagement and disengagement based on photo- and thermally driven cis–trans isomerization at the PtII centre. This molecular rotary motion transmitter has been constructed from two coordinating azaphosphatriptycene rotators and one PtII ion as a stator. Isomerization between an engaged cis-form and a disengaged trans-form is reversibly driven by ultraviolet irradiation and heating. Such a photo- and thermally triggered motional interconversion between engaged/disengaged states on a metal ion would provide a selector switch for more complex interlocking systems.
Gears are found rarely in animals and have never been reported to intermesh and rotate functionally like mechanical gears.
We now demonstrate functional gears in the ballistic jumping movements of the flightless planthopper insect Issus. The nymphs, but not adults, have a row of cuticular gear (cog) teeth around the curved medial surfaces of their two hindleg
trochantera. The gear teeth on one trochanter engaged with and sequentially moved past those on the other trochanter during
the preparatory cocking and the propulsive phases of jumping. Close registration between the gears ensured that both hindlegs
moved at the same angular velocities to propel the body without yaw rotation. At the final molt to adulthood, this synchronization
mechanism is jettisoned.
The synthesis and single-molecule imaging of two inherently fluorescent nanocars equipped with adamantane wheels is reported. The nanocars were imaged using 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) as the chromophore, which was rigidly incorporated into the nanocar chassis via Sonogashira cross-coupling chemistry that permitted the synthesis of nanocars having different geometries. In particular, studied here were 4- and 3-wheeled nanocars with adamantane wheels. It was found that for the 4-wheeled nanocar, the percentage of moving nanocars and the diffusion constant show a significant improvement over p-carborane-wheeled nanocars with the same chassis. The 3-wheeled nanocar showed only limited mobility due to its geometry. These results are consistent with a requisite wheel-like rolling motion. We furthermore developed a model that relates the percentage of moving nanocars in single-molecule experiments with the diffusion constant. The excellent agreement between the model and the new results presented here as well as previous single-molecule studies of fluorescent nanocars yields an improved understanding of motion in these molecular machines.
Propelling single molecules in a controlled manner along an unmodified surface remains extremely challenging because it requires molecules that can use light, chemical or electrical energy to modulate their interaction with the surface in a way that generates motion. Nature's motor proteins have mastered the art of converting conformational changes into directed motion, and have inspired the design of artificial systems such as DNA walkers and light- and redox-driven molecular motors. But although controlled movement of single molecules along a surface has been reported, the molecules in these examples act as passive elements that either diffuse along a preferential direction with equal probability for forward and backward movement or are dragged by an STM tip. Here we present a molecule with four functional units--our previously reported rotary motors--that undergo continuous and defined conformational changes upon sequential electronic and vibrational excitation. Scanning tunnelling microscopy confirms that activation of the conformational changes of the rotors through inelastic electron tunnelling propels the molecule unidirectionally across a Cu(111) surface. The system can be adapted to follow either linear or random surface trajectories or to remain stationary, by tuning the chirality of the individual motor units. Our design provides a starting point for the exploration of more sophisticated molecular mechanical systems with directionally controlled motion.
The design of a single-molecule machine consisting of functional components requires a detailed understanding of its mechanical motion. The scanning tunnelling microscope (STM) is the only available tool for driving and imaging such a nanoscale machine on a surface. Both lateral hopping motions and conformational changes of single molecules can be induced using the STM tip. However, no rolling of a wheel has been demonstrated so far at the nanoscale, even though this is a very useful motion at the macroscopic scale. Here we show how the rolling of a single molecule equipped with two wheels (0.8 nm in diameter) can be induced by the STM tip. The characteristics of the rolling are recorded in the STM feedback loop manipulation signal and in real time. We capture unambiguous signatures of the conformational change happening during the rolling. Our approach of controlling the intramolecular mechanics provides a path towards the bottom-up assembly of more complex molecular machines.
Biological rotary motors can alter their mechanical function by changing the direction of rotary motion. Achieving a similar reversal of direction of rotation in artificial molecular motors presents a fundamental stereochemical challenge: how to change from clockwise to anticlockwise motion without compromising the autonomous unidirectional rotary behaviour of the system. A new molecular motor with multilevel control of rotary motion is reported here, in which the direction of light-powered rotation can be reversed by base-catalysed epimerization. The key steps are deprotonation and reprotonation of the photochemically generated less-stable isomers during the 360° unidirectional rotary cycle, with complete inversion of the configuration at the stereogenic centre. The ability to change directionality is an essential step towards mechanical molecular systems with adaptive functional behaviour.
We report the incrementally staged design, synthesis, characterization, and operation of a molecular machine that behaves like a nanoscale elevator. The operation of this device, which is made of a platformlike component interlocked with a trifurcated riglike component and is only 3.5 nanometers by 2.5 nanometers in size, relies on the integration of several structural and functional molecular subunits. This molecular elevator is considerably more complex and better organized than previously reported artificial molecular machines. It exhibits a clear-cut on-off reversible behavior, and it could develop forces up to around 200 piconewtons.
Molecular motors are at the heart of cellular machinery, and they are involved in converting chemical and light energy inputs into efficient mechanical work. From a synthetic perspective, the most advanced molecular motors are rotators that are activated by light wherein a molecular subcomponent rotates unidirectionally around an axis. The mechanical work produced by arrays of molecular motors can be used to induce a macroscopic effect. Light activation offers advantages over biological chemically activated molecular motors because one can direct precise spatiotemporal inputs while conducting reactions in the gas phase, in solution and in vacuum, while generating no chemical byproducts or waste. In this review, we describe the origins of the first light-activated rotary motors and their modes of function, the structural modifications that led to newer motor designs with optimized rotary properties at variable activation wavelengths. Presented are molecular motor attachments to surfaces, their insertion into supramolecular structures and photomodulating materials, their use in catalysis, and their action in biological environments to produce exciting new prospects for biomedicine.
A dissymmetric piano-stool ruthenium(II) complex bearing different halogens on the rotor part was efficiently prepared and subsequently used as key building block in the modular synthesis of potential rotative molecular machines via palladium-catalysed “Sonogashira/Suzuki-Miyaura” sequences. Applying this novel synthetic route to various cross-coupling partners, prototypes of potential molecular winches and cogwheel for gears application specifically designed for studies at the single-molecule scale were efficiently obtained.
The design and synthesis of two families of molecular gears prototypes is reported, with the aim of assembling them into trains of gears on surface and ultimately achieving controlled intermolecular gearing motion. These piano‐stool ruthenium complexes incorporate a hydrotris(indazolyl)borate moiety as tripodal rotation axle and a pentaarylcyclopentadienyl ligand as star‐shaped cogwheel, equipped with five teeth ranging from pseudo 1‐dimensional aryl groups to large planar 2‐dimensional paddles. A divergent synthetic approach was followed, starting from a penta(p‐bromophenyl)cyclopentadienyl ruthenium(II) complex as key precursor or from its iodinated counterpart, first obtained by copper‐catalyzed aromatic Br/I exchange. Subsequent five‐fold cross‐coupling reactions with various partners allowed high structural diversity to be reached, yielding molecular gears prototypes displaying aryl‐, carbazole‐, BODIPY‐ and porphyrin‐derived teeth of increasing size and length.
Two molecule-gears, 1.2 nm in diameter with 6 teeth, are mounted each on a single copper ad-atom separated exactly by 1.9 nm on a lead surface using a low temperature scanning tunneling microscope (LT-STM). A functioning train of 2 molecule-gears is constructed completed with a molecule-handle. Not mounted on a Cu ad-atom axle, this ancillary molecule-gear is mechanically engaged with the first molecule-gear of the train to stabilize its step by step rotation. Centered on its Cu ad-atom axle, the rotation of the first gear of the train step by step rotates the second similar to a train of macroscopic gears. From the handle to the first and to this second molecule-gear, the exact positioning of the two Cu ad-atom axles on the lead surface ensures that the molecular teeth to teeth mechanics is fully reversible.
Directed motion at the nanoscale is a central attribute of life, and chemically driven motor proteins are nature's choice to accomplish it. Motivated and inspired by such bionanodevices, in the past few decades chemists have developed artificial prototypes of molecular motors, namely, multicomponent synthetic species that exhibit directionally controlled, stimuli-induced movements of their parts. In this context, photonic and redox stimuli represent highly appealing modes of activation, particularly from a technological viewpoint. Here we describe the evolution of the field of photo- and redox-driven artificial molecular motors, and we provide a comprehensive review of the work published in the past 5 years. After an analysis of the general principles that govern controlled and directed movement at the molecular scale, we describe the fundamental photochemical and redox processes that can enable its realization. The main classes of light- and redox-driven molecular motors are illustrated, with a particular focus on recent designs, and a thorough description of the functions performed by these kinds of devices according to literature reports is presented. Limitations, challenges, and future perspectives of the field are critically discussed.
This highlight review describes our contribution to the field of biomimetic and technomimetic molecular machines specially designed to be studied as single molecules on surfaces. Prototypes of molecular wheels, vehicles, gears and motors will be described from their design to the study of their controlled motions using ultra-high-vacuum low-temperature scanning tunneling microscopes (UHV-LT-STM).
Major improvements in the synthesis of surface‐mounted rotary molecular machines based on ruthenium(II) complexes are reported. The development of a one‐pot indium(III)‐mediated "N‐deprotection / ester reductive sulfidation" sequence allowed step economy, reproducibility and high efficiency in the synthesis of the thioether‐functionalized tripodal ligand. Switching to the thallium salt of hydrotris(indazolyl)borate and to microwave heating further optimized the preparation of the common intermediate in the modular synthesis of symmetric and dissymmetric molecular motors and gears. The penta(4‐bromophenyl)cyclopentadienyl ruthenium(II) key precursor is now reproducibly synthesized in 5 steps and 31% overall yield on the longest linear sequence. Subsequent five‐fold Suzuki‐Miyaura coupling with ferroceneboronic acid led to a new C5‐symmetric penta‐ferrocenyl molecular motor.
Chemistry welcomes a new bond: The mechanical bond has endowed molecules with component parts whose movements can be controlled and monitored. In his Nobel Lecture, J. F. Stoddart describes how being able to template the formation of mechanically interlocked molecules has led to the design and synthesis of shuttles, switches, and machines at the nanoscale.
A journey into the nano-world: The ability to design, use and control motor-like functions at the molecular level sets the stage for numerous dynamic molecular systems. In his Nobel lecture, B. L. Feringa describes the evolution of the field of molecular motors and explains how to program and control molecules by incorporating responsive and adaptive properties.
To a large extent, the field of "molecular machines" started after several groups were able to prepare, reasonably easily, interlocking ring compounds (named catenanes for compounds consisting of interlocking rings and rotaxanes for rings threaded by molecular filaments or axes). Important families of molecular machines not belonging to the interlocking world were also designed, prepared, and studied but, for most of them, their elaboration was more recent than that of catenanes or rotaxanes. Since the creation of interlocking ring molecules is so important in relation to the molecular machinery area, we will start with this aspect of our work. The second part will naturally be devoted to the dynamic properties of such systems and to the compounds for which motions can be directed in a controlled manner from the outside, that is, molecular machines. We will restrict our discussion to a very limited number of examples which we consider as particularly representative of the field.
Motor proteins are nature's solution for directing movement at the molecular level. The field of artificial molecular motors takes inspiration from these tiny but powerful machines. Although directional motion on the nanoscale performed by synthetic molecular machines is a relatively new development, significant advances have been made. In this review an overview is given of the principal designs of artificial molecular motors and their modes of operation. Although synthetic molecular motors have also found widespread application as (multistate) switches, we focus on the control of directional movement, both at the molecular scale and at larger magnitudes. We identify some key challenges remaining in the field.
Invited for the cover of this issue is the group of Gwénaël Rapenne and Claire Kammerer from CEMES-CNRS at University Paul Sabatier, Toulouse, France. The cover image shows the use of scorpionates to anchor nanomachines on metal surfaces for mechanical applications such as unidirectional rotation (for motors) or power transmission (for gears).
A range of artificial molecular systems has been created that can exhibit controlled linear and rotational motion. In the further development of such systems, a key step is the addition of communication between molecules in a network. Here, we show that a two-dimensional array of dipolar molecular rotors can undergo simultaneous rotational switching when applying an electric field from the tip of a scanning tunnelling microscope. Several hundred rotors made from porphyrin-based double-decker complexes can be simultaneously rotated when in a hexagonal rotor network on a Cu(111) surface by applying biases above 1 V at 80 K. The phenomenon is observed only in a hexagonal rotor network due to the degeneracy of the ground-state dipole rotational energy barrier of the system. Defects are essential to increase electric torque on the rotor network and to stabilize the switched rotor domains. At low biases and low initial rotator angles, slight reorientations of individual rotors can occur, resulting in the rotator arms pointing in different directions. Analysis reveals that the rotator arm directions are not random, but are coordinated to minimize energy via crosstalk among the rotors through dipolar interactions.
This microreview describes the use of scorpionate hydrotris(indazolyl)borate ligands to build structurally rigid bifunctional surface-mounted molecular gears or motors. The article starts with the synthesis of 6-functionalized indazoles and their corresponding scorpionate tris(indazolyl)borate tripodal ligands. Thioether groups allow the tripodal anchoring of such ligands on metallic surfaces, whereas ester functions enable anchoring on insulating surfaces. Finally, we present their coordination to ruthenium penta(aryl)cyclopentadienyl fragments for the preparation of prototypes of molecular gears and motors. The synthesis of the tetraferrocenylruthenium complex, a molecular motor that has been shown to exhibit controlled clockwise or anticlockwise unidirectional rotation, is also detailed.
Reaction of pyrrole and an aromatic aldehyde at room temperature affords the corresponding tetraarylporphyrinogen in high yield at thermodynamic equilibrium. Oxidation yields the porphyrin. The reaction conditions are of broad scope.
A molecular analog of a wheelbarrow is synthesized following a strategy based on sequential double Knoevenagel and Diels–Alder reactions.
Technomimetic molecules are molecules designed to imitate macroscopic objects at the molecular level, also transposing the motions that these objects are able to undergo. This article focuses on the synthesis of two polyaromatic hydrocarbons designed by analogy with macroscopic wheelbarrows. The molecular wheelbarrows are synthesized following a modular strategy based on sequential double Knoevenagel and Diels–Alder reactions. Our strategy allowed to easily vary the chemical nature of the handles, which is crucial for subsequent manipulation with an STM tip.
The design, synthesis, and running of a molecular nanovehicle on a surface assisted by proper nanocommunication channels for feeding and guiding the vehicle now constitute an active field of research and are no longer a nano-joke. In this Perspective, we describe how this field began, its growth, and problems to be solved. Better molecular wheels, a molecular motor with its own gears assembling for torque transmission must be mounted on (i.e., chemically bonded to) a good molecular chassis for the resulting covalently constructed molecular nanovehicle to run on a surface in a controlled manner at the atomic scale. We propose a yearly molecule concept nanocar contest to boost molecular nanovehicle research.
The design of artificial molecular machines often takes inspiration from macroscopic machines. However, the parallels between the two systems are often only superficial, because most molecular machines are governed by quantum processes. Previously, rotary molecular motors powered by light and chemical energy have been developed. In electrically driven motors, tunnelling electrons from the tip of a scanning tunnelling microscope have been used to drive the rotation of a simple rotor in a single direction and to move a four-wheeled molecule across a surface. Here, we show that a stand-alone molecular motor adsorbed on a gold surface can be made to rotate in a clockwise or anticlockwise direction by selective inelastic electron tunnelling through different subunits of the motor. Our motor is composed of a tripodal stator for vertical positioning, a five-arm rotor for controlled rotations, and a ruthenium atomic ball bearing connecting the static and rotational parts. The directional rotation arises from sawtooth-like rotational potentials, which are solely determined by the internal molecular structure and are independent of the surface adsorption site.
A 1,3-alternate calix[4]arene bearing a nitrogen-containing crown cap at one side and a bis(ethoxyethoxy) group at another side has been synthesized. 1H NMR spectroscopic studies showed that Ag+ is bound to the crown-capped side (log Kass. = 9.78: CD2Cl2:CD3OD = 4:1 v/v, 30 °C), and the dissociation of Ag+ from this cavity is very slow. When the nitrogen atom in the crown ring is protonated with trifluoroacetic acid, Ag+ is pushed out to the bis(ethoxyethoxy) side through a π-basic tube of the 1,3-alternate calix[4]arene. The dissociation of the complex from the bis(ethoxyethoxy) side occurs relatively fast. On the other hand, when the nitrogen·H+ in the crown ring is deprotonated with Li2CO3 and diazabicycloundecene, Ag+ is sucked back to the crown-capped side through the π-basic tube. These chemically-switchable actions well imitate the function of a “syringe”, using the π-basic tube as a pipette and the crown ring as a rubber cap. We believe that this prototype of a “molecular syringe” is a novel molecular architecture for the action of metal cations.
The title compound was prepared by the thermolysis in perfluorodecalin of 1-triptycyl 1-triptyceneperoxycarboxylate which in turn was obtained by the reaction of 1-triptycyllithium with oxygen followed by treatment with 1-triptycenecarbonyl chloride. No sign of restricted rotation around the bridgehead-to-oxygen bonds of the ether was indicated by the 1H and 13C NMR spectra in spite of its overcrowded molecular framework.
The future's wheel: A new class of wheels, based on subphthalocyanine fragments, for future incorporation in functional nanovehicles is reported (see figure). The syntheses of a symmetric wheel, a nitrogen-tagged wheel, and their ethynyl-bridged homodimers are presented. Theoretical calculations and STM imaging demonstrate the advantage of a bowl-shaped structure and the efficiency of the tag for STM imaging.
We have studied the deposition and imaging of nanoscale molecular wheelbarrows. These molecules integrate-in analogy to macroscopic barrows-two wheels, legs and handles along a polyaromatic platform and were imaged on a clean Cu(100) surface with a scanning tunneling microscope at 7 K. The obtained images are in accordance with calculations and are dominated by the wheels. Several stable conformations of the wheelbarrow were found and identified by comparison with calculated images. (c) 2005 Elsevier B.V. All rights reserved.
Two new nanovehicles that have extended aromatic platforms as the cargo zones have been obtained. Two strategies were considered for the formation of the perylene core from two naphthalene precursors. The first was based on a Scholl-type reaction involving an oxidant, and the second used a brominated derivative to perform a homocoupling reaction. The first strategy failed under diverse coupling conditions in the presence of several strong oxidants. Nevertheless, the use of CoF(3) in trifluoroacetic acid triggered a dimerization reaction between two ester groups of one molecule and the naphthalene unit of another, thereby surprisingly yielding a ten-membered carbon macrocycle. The second strategy encountered a lack of reactivity of the substrate under several homocoupling conditions. The dimerization was not easily performed but Ullmann-type conditions ultimately gave the expected product. The low yield and low solubility of the product encouraged us to modify our initial design. The synthesis of a new chassis that incorporated additional tert-butyl groups improved the solubility of the molecules and also prevented overcyclization of the aromatic platform by blocking these positions. Some p-phenylene spacers were also intercalated between the iodine and perylene centers to increase the reactivity of the halide towards coupling reactions. Two new chassis were obtained by Scholl-type oxidative coupling using FeCl(3) as the oxidant. The introduction of four triptycene wheels allowed the formation of the two corresponding nanovehicles.
Dynamic gearing of molecular spur gears, the most common type of mechanical gear, is elucidated. Molecular design and conformational analysis show that derivatives of 4,4-bis(triptycen-9-ylethynyl)bibenzimidazole represent suitable constructs to investigate gearing behavior of collateral triptycene (Tp) groups. To test this design, DFT calculations (B97-D/Def2-TZVP) were employed and the results suggest that these molecules undergo geared rotation preferentially to gear slippage. Synthesis of derivatives was carried out, providing a series of molecular spur gears, including the first desymmetrized spur gear molecules, which were subsequently subjected to stereochemical analysis.
For molecules to be used as components in molecular machines, methods that couple individual molecules to external energy sources and that selectively excite motion in a given direction are required. Significant progress has been made in the construction of molecular motors powered by light and by chemical reactions, but electrically driven motors have not yet been built, despite several theoretical proposals for such motors. Here we report that a butyl methyl sulphide molecule adsorbed on a copper surface can be operated as a single-molecule electric motor. Electrons from a scanning tunnelling microscope are used to drive the directional motion of the molecule in a two-terminal setup. Moreover, the temperature and electron flux can be adjusted to allow each rotational event to be monitored at the molecular scale in real time. The direction and rate of the rotation are related to the chiralities of both the molecule and the tip of the microscope (which serves as the electrode), illustrating the importance of the symmetry of the metal contacts in atomic-scale electrical devices.
This tutorial review presents our strategy to control the rotation in a molecular rotary motor, and the family of star-shaped ruthenium complexes designed to perform such a task. The molecules have a piano-stool structure with a "stator" meant to be grafted on a surface, and a "rotor" bearing redox-active groups, so that addressing the molecule with nano-electrodes would trigger rotation.
Gears are microfabricated down to diameters of a few micrometres. Natural macromolecular motors, of tens of nanometres in diameter, also show gear effects. At a smaller scale, the random rotation of a single-molecule rotor encaged in a molecular stator has been observed, demonstrating that a single molecule can be rotated with the tip of a scanning tunnelling microscope (STM). A self-assembled rack-and-pinion molecular machine where the STM tip apex is the rotation axis of the pinion was also tested. Here, we present the mechanics of an intentionally constructed molecule-gear on a Au(111) surface, mounting and centring one hexa-t-butyl-pyrimidopentaphenylbenzene molecule on one atom axis. The combination of molecular design, molecular manipulation and surface atomic structure selection leads to the construction of a fundamental component of a planar single-molecule mechanical machine. The rotation of our molecule-gear is step-by-step and totally under control, demonstrating nine stable stations in both directions.
The drive to miniaturize devices has led to a variety of molecular machines inspired by macroscopic counterparts such as molecular motors, switches, shuttles, turnstiles, barrows, elevators, and nanovehicles. Such nanomachines are designed for controlled mechanical motion and the transport of nanocargo. As researchers miniaturize devices, they can consider two complementary approaches: (1) the “top-down” approach, which reduces the size of macroscopic objects to reach an equivalent microscopic entity using photolithography and related techniques and (2) the “bottom-up” approach, which builds functional microscopic or nanoscopic entities from molecular building blocks. The top-down approach, extensively used by the semiconductor industry, is nearing its scaling limits. On the other hand, the bottom-up approach takes advantage of the self-assembly of smaller molecules into larger networks by exploiting typically weak molecular interactions. But self-assembly alone will not permit complex assembly. Using nanomachines, we hope to eventually consider complex, enzyme-like directed assembly. With that ultimate goal, we are currently exploring the control of nanomachines that would provide a basis for the future bottom-up construction of complex systems.
Attempts to fabricate mechanical devices on the molecular level have yielded analogues of rotors, gears, switches, shuttles, turnstiles and ratchets. Molecular motors, however, have not yet been made, even though they are common in biological systems. Rotary motion as such has been induced in interlocked systems and directly visualized for single molecules, but the controlled conversion of energy into unidirectional rotary motion has remained difficult to achieve. Here we report repetitive, monodirectional rotation around a central carbon-carbon double bond in a chiral, helical alkene, with each 360 degrees rotation involving four discrete isomerization steps activated by ultraviolet light or a change in the temperature of the system. We find that axial chirality and the presence of two chiral centres are essential for the observed monodirectional behaviour of the molecular motor. Two light-induced cis-trans isomerizations are each associated with a 180 degrees rotation around the carbon-carbon double bond and are each followed by thermally controlled helicity inversions, which effectively block reverse rotation and thus ensure that the four individual steps add up to one full rotation in one direction only. As the energy barriers of the helicity inversion steps can be adjusted by structural modifications, chiral alkenes based on our system may find use as basic components for 'molecular machinery' driven by light.
The conversion of energy into controlled motion plays an important role in both man-made devices and biological systems. The principles of operation of conventional motors are well established, but the molecular processes used by 'biological motors' such as muscle fibres, flagella and cilia to convert chemical energy into co-ordinated movement remain poorly understood. Although 'brownian ratchets' are known to permit thermally activated motion in one direction only, the concept of channelling random thermal energy into controlled motion has not yet been extended to the molecular level. Here we describe a molecule that uses chemical energy to activate and bias a thermally induced isomerization reaction, and thereby achieve unidirectional intramolecular rotary motion. The motion consists of a 120 degrees rotation around a single bond connecting a three-bladed subunit to the bulky remainder of the molecule, and unidirectional motion is achieved by reversibly introducing a tether between the two units to energetically favour one of the two possible rotation directions. Although our system does not achieve continuous and fast rotation, the design principles that we have used may prove relevant for a better understanding of biological and synthetic molecular motors producing unidirectional rotary motion.
The first example of "light-driven chiral molecular scissors" (1), which consists of 1,1',3,3'-tetraarylferrocene as a pivot part and azobenzene as a driving part, was synthesized. Absorption, circular dichroism (CD), and 1H NMR spectral studies on the photoinduced isomerization process of an enantiomer of 1 agreed well with a prediction by a DFT calculation, where a motion of the handles via light-driven contraction/expansion of the connecting azobenzene strap was transformed, through a pivotal motion of the ferrocene unit, into an open-close motion of the blade parts.
Four caltrop-shaped molecules that might be useful as surface-bound electric field-driven molecular motors have been synthesized. The caltrops are comprised of a pair of electron donor-acceptor arms and a tripod base. The molecular arms are based on a carbazole or oligo(phenylene ethynylene) core with a strong net dipole. The tripod base uses a silicon atom as its core. The legs of the tripod bear sulfur-tipped bonding units, as acetyl-protected benzylic thiols, for bonding to a gold surface. The geometry of the tripod base allows the caltrop to project upward from a metallic surface after self-assembly. Ellipsometric studies show that self-assembled monolayers of the caltrops are formed on Au surfaces with molecular thicknesses consistent with the desired upright-shaft arrangement. As a result, the zwitterionic molecular arms might be controllable when electric fields are applied around the caltrops, thereby constituting field-driven motors.
The circumrotation of a submolecular fragment in either direction in a synthetic molecular structure is described. The movement of a small ring around a larger one occurs through positional displacements arising from biased Brownian motion that are kinetically captured and then directionally released. The sense of rotation is governed solely by the order in which a series of orthogonal chemical transformations is performed. The minimalist nature of the [2]catenane flashing ratchet design permits certain mechanistic comparisons with the Smoluchowski-Feynman ratchet and pawl. Even when no work has to be done against an opposing force and no net energy is used to power the motion, a finite conversion of energy is intrinsically required for the molecular motor to undergo directional rotation. Nondirectional rotation has no such requirement.
With the hope of directing future bottom-up fabrication through bulk external stimuli (such as electric fields) on nanometer-sized transporters, we sought to study controlled molecular motion on surfaces through the rational design of surface-capable molecular structures called nanocars. Here we show that the observed movement of the nanocars is a new type of fullerene-based wheel-like rolling motion, not stick-slip or sliding translation, due to evidence including directional preference in both direct and indirect manipulation and studies of related molecular structures.
Empirical force-field calculations show that bis(9-triptycyl)methane has a C(s) ground state and that the securely meshed triptycyl groups undergo nearly unhindered cogwheel rotation through a C(2) transition state, with an activation energy of approximately 1.0 kcal mol(-1). These features lead to note-worthy stereochemical attributes in appropriately substituted derivatives and analogs. Bis(9-triptycyl)carbinol has been prepared as an example of a compound that is chemically achiral, even though all conformations are chiral under the constraint of gear meshing. It is shown that, under the same constraint, ring substitution of either compound (or analogous systems) may lead to residual stereoisomerism. A permutational analysis of chemical isomers and isomerizations for every possible type of substitution pattern gives an enumeration of residual stereoisomers under the operation of various gearing and nongearing modes and provides information essential for a choice among mechanistic alternatives for a given isomer count.
Molecular machines, and in particular molecular motors with synthetic molecular structures and fuelled by external light, voltage or chemical conversions, have recently been reported. Most of these experiments are carried out in solution with a large ensemble of molecules and without access to one molecule at a time, a key point for future use of single molecular machines with an atomic scale precision. Therefore, to experiment on a single molecule-machine, this molecule has to be adsorbed on a surface, imaged and manipulated with the tip of a scanning tunnelling microscope (STM). A few experiments of this type have described molecular mechanisms in which a rotational movement of a single molecule is involved. However, until now, only uncontrolled rotations or indirect signatures of a rotation have been reported. In this work, we present a molecular rack-and-pinion device for which an STM tip drives a single pinion molecule at low temperature. The pinion is a 1.8-nm-diameter molecule functioning as a six-toothed wheel interlocked at the edge of a self-assembled molecular island acting as a rack. We monitor the rotation of the pinion molecule tooth by tooth along the rack by a chemical tag attached to one of its cogs.
A combination of solid-state 13C CPMAS NMR, 2H NMR, X-ray-determined anisotropic displacement parameters (ADPs), and molecular mechanics calculations were used to analyze the rotational dynamics of 1,4-bis[3,3,3-tris(m-methoxyphenyl)propynyl]benzene (3A), a structure that emulates a gyroscope with a p-phenylene group acting as a rotator and two m-methoxy-substituted trityl groups acting as a stator. The line shape analysis of VT 13C CPMAS and broad-band 2H NMR data were in remarkable agreement with each other, with rotational barriers of 11.3 and 11.5 kcal/mol, respectively. The barriers obtained by analysis of ADPs obtained by single-crystal X-ray diffraction at 100 and 200 K, assuming a sinusoidal potential, were 10.3 and 10.1 kcal, respectively. A similar analysis of an X-ray structure solved from data acquired at 300 K suggested a barrier of only 8.0 kcal/mol. Finally, a rotational potential calculated with a finite cluster model using molecular mechanics revealed a symmetric but nonsinusoidal potential that accounts relatively well for the X-ray-derived values and the NMR experimental results. It is speculated that the discrepancy between the barriers derived from low and high-temperature X-ray data may be due to an increase in anharmonicity, or to disorder, at the higher temperature values.
World’s first nanocar race: a single molecule piloted per team
- G Rapenne
- C Joachim
STM Manipulation of boron-subphthalocyanine nano-wheel dimers on Au(111)
- A Nickel
- J Meyer
- R Ohmann
- H.-P Jacquot De Rouville
- G Rapenne
- C Joachim
- G Cuniberti
- F Moresco