Light-driven Molecular Motors Research Articles

Theoretical Study of Topographical Features around the Conical Intersections of 9-(2-Cyclopenten-1-ylidene)-9H-fluorene

Ab initio molecular orbital calculations have been performed to examine the topographical features around the conical intersections (CIXs) for the photoisomerization of 9-(2-cyclopenten-1-ylidene)-9H-fluorene (CPF). The present study is motivated by the computational findings of the topographical features in the CIX region of a fluorene-based light-driven molecular motor with smooth rotation (denoted by M5-PCPF). CPF is a parent molecule of M5-PCPF but exhibits neither helicity nor unidirectionality. A stable geometry in S1 (S1-geometry) is located in the region where the ethylenic rotary axis is perpendicularly twisted, but the fluorene part wags little against the rotary axis, as is the case of M5-PCPF. However, the topographical features around the CIXs of CPF are different from those of M5-PCPF. The wagging motion of the fluorene stator to the negative direction from S1-geometry leads straight to a CIX which implements forward and backward rotations. On the other hand, only the wagging motion to the positive direction does not lead to a CIX, and additional geometrical deformations are needed. Depending on the directions of additional geometrical deformations, two CIXs, which play the roles of respective exit channels for forward and backward rotations, are located in the positive wagging region. The difference in the topographical features in the CIX region between CPF and M5-PCPF is ascribed to the effect of the pentamethylene chain. By virtue of much less computational labor of CPF as well as the electronic structures being similar to those of M5-PCPF, the intrinsic reaction coordinate was followed from the ethylenic ππ* state at the stable geometry in S0 into S1-geometry. Thereby, it was confirmed that a spectroscopically dark state due to the π(fluorene)π*(ethylene) excitation contributes less to the photochemical process of the ethylenic bond torsion, as is the case of M5-PCPF.

Theoretical Study of Topographical Features around the Conical Intersections of Fluorene-Based Light-Driven Molecular Rotary Motor

Topographical features around the conical intersection (CIX) of a fluorene-based light-driven molecular rotary motor have been examined by means of ab initio molecular orbital calculations. The model molecule is a derivative of 9-(2-phenyl-2-cyclopenten-1-ylidene)-9H-fluorene (PCPF) where PCPF is bridged by a pentamethylene chain between the 2 position of the phenyl group and the pseudoaxial position of the C(5) atom in the 2-cyclopenten-1-ylidene ring. This model molecule (denoted by M5-PCPF) has been very recently reported as a candidate for a light-driven molecular motor with constant rotation. The conical intersection for the photoprocess of the ethylenic C═C torsion reported there (denoted by CIX1), which exclusively leads to a product of P'-M5-PCPF, is found to be classified as a sloped-type CIX. Another CIX reported at the present time (CIX2) exclusively goes back to a reactant of P-M5-PCPF, whereas CIX2 is also classified as a sloped-type CIX. At the stable geometry in S1 around the CIX region (S1-geometry), the 2-cyclopenten-1-ylidene rotor takes a perpendicular twist against the fluorene stator, but the fluorene stator does not wag so much against the C═C rotary axis. The wagging motions of the fluorene stator from S1-geometry to the opposite directions lead to CIX1 and CIX2, respectively.

Silanization of quartz, silicon and mica surfaces with light-driven molecular motors: construction of surface-bound photo-active nanolayers

The attachment of molecular rotary motors containing triethoxysilane functional groups to quartz, silicon and mica surfaces is described. Motors containing silane coupling agents in their structure form stable molecular layers on quartz and silicon surfaces. Motors attached to these surfaces were found to undergo photochemical and thermal isomerization steps similar to those observed in solution. Additionally, successful formation of molecular "carpets" on atomically flat mica extending micrometer-sized length scales is presented. These "carpets" were found to undergo morphological changes upon irradiation with UV-light.

Synthesis of peptide-conjugated light-driven molecular motors and evaluation of their DNA-binding properties

Synthetic light-driven molecular motors are molecular machines capable of rotation under photo-irradiation. In this paper, we report the synthesis of peptide-conjugated molecular motors and evaluate their DNA-binding properties.

Ultrafast ignition of a uni-directional molecular motor

Light-driven molecular motors convert light into mechanical energy via excited state reactions. In this work we follow sub-picosecond primary events in the cycle of a two-stroke unidirectional motor by fluorescence up-conversion and transient absorption.

Effect of Temperature on the Surface Relief Grating Formation caused by Rotation of Light-driven Molecular Motor

Effect of Temperature on the Surface Relief Grating Formation caused by Rotation of Light-driven Molecular Motor

Theoretical Design of a Fluorene-Based Light-Driven Molecular Rotary Motor with Constant Rotation

A fluorene-based light-driven molecular rotary motor with constant rotation has been designed by means of ab initio molecular orbital calculations. A model molecule is obtained by a chemical modification of 9-(5-methyl-2-phenyl-2-cyclopenten-1-ylidene)-9H-fluorene (MPCPF) which we reported recently. Despite that MPCPF has a great advantage that the thermal helical inversion proceeds with a much lower energy barrier than those in previous model molecules, a small energy difference between the M- and the P-helical isomers is possible to cause a fast equilibration between them after electronic relaxation around the conical intersection (CIX), and therefore, a backward rotation from the M-helical isomer is not always suppressed effectively. In order to overcome this defect of MPCPF, we modified MPCPF by a bridge of a pentamethylene chain between the 2 position of the phenyl group and the psesudoaxial position of the C(5) atom in the 2-cyclopenten-1-ylidene ring. The modified molecule with a pentamethylene bridge (denoted by M5-PCPF) energetically destabilizes a conformation in the M-helical region and so passes through the M-helical region without any trap in the full rotary process, which leads to direct conversion from a stable P-helical isomer to another stable P-helical isomer via CIX. Therefore, M5-PCPF is expected to be a light-driven molecular rotary motor with constant rotation speed as well as unidirectionality.

Molecular motor speed limits

To improve the efficiency of molecular motors, a better understanding of the dynamics of their functional motions is required. Now, ultrafast fluorescence spectroscopy has been used to monitor the excited-state evolution of a light-driven molecular motor.

Molecular switches and cages

Molecular switches can toggle between two (or more) stable states encoding different physical features. They allow complex systems to respond to changes in their environment defined by light intensity, pH, temperature or voltage. As such, molecular switches play a key role in biology and information technology and have become important components of advanced materials. Chemists have developed a large number of synthetic switches, complementing the many types found in nature. Given their prominence in biology, it is not surprisingly that photoswitches, which are actuated by ultraviolet, visible or infrared light, have been an especially productive field of study. Despite their long history, new types of synthetic photoswitches continue to emerge and “old friends”, such as azobenzenes are constantly improved and optimized. This is not only true with respect to their photophysical properties but also with regard to their synthetic accessibility. Indeed, as molecular switches are applied in ever-increasing quantities, the efficiency of their syntheses becomes a primary concern, requiring the development of new synthetic methods and strategies. The corresponding results, however, are often buried in the Supporting Information of papers that focus on functional aspects, which does not reflect the relative effort that goes into the design and synthesis of these molecules. Caged compounds are a subclass of (photo)switches that have special functional features. As opposed to “true” switches, they can only be turned ON and the abatement of their activity depends on secondary processes (such as diffusion from the active zone or, more importantly, re-uptake systems). In terms of their biological application, especially in neurobiology, they are much further developed than reversibly switchable molecules. For instance, two-photon activation, which allows for very precise localization, is fairly well established with caged compounds but in its infancy in the case of reversible photoswitches. The present Thematic Series of the Beilstein Journal of Organic Chemistry addresses the crucial role that chemistry, and particularly organic chemistry, can play in tuning the functional features of molecular switches and cages. These features include their absorption spectra, conductivity, geometry and bistability, as well as their polarity, solubility, efficacy, or catalytic activity. Photoswitches are covered extensively, ranging from diarylethenes (Pu, Wagenknecht) to dihydroazulenes/vinylheptafulvenes (Nielsen) and azobenzenes (Ruck-Braun, Hoppmann). Two reviews discuss cis-azobenzenes with rapid thermal isomerization kinetics (Velasco), and highlight the azobenzene moiety as one of the smallest light-driven molecular motors conceivable (Merino). Issues of bistability are also addressed in an account on shape-persistent, optically active macrocycles (Pasini). Molecular switches that respond to changes in pH are covered as well (Haberhauer and Aprahamian), reflecting their importance in biology and in materials science. Finally, switching is highlighted as a synthetic strategy for building advanced materials that are useful in photovoltaics (Matile). Chemists, by nature, like to control things and probably actuate macroscopic switches more often than the average person. We hope that this collection of papers will motivate some of our colleagues to also consider nanoscopic versions of switches (and cages). For those of us who deal with these molecules on a daily basis, this Thematic Series will hopefully provide further inspiration and an impetus to continue work in this fascinating field of research. Dirk Trauner Munich, June 2012

Ultrafast dynamics in the power stroke of a molecular rotary motor

Light-driven molecular motors convert light into mechanical energy through excited-state reactions. Unidirectional rotary molecular motors based on chiral overcrowded alkenes operate through consecutive photochemical and thermal steps. The thermal (helix inverting) step has been optimized successfully through variations in molecular structure, but much less is known about the photochemical step, which provides power to the motor. Ultimately, controlling the efficiency of molecular motors requires a detailed picture of the molecular dynamics on the excited-state potential energy surface. Here, we characterize the primary events that follow photon absorption by a unidirectional molecular motor using ultrafast fluorescence up-conversion measurements with sub 50 fs time resolution. We observe an extraordinarily fast initial relaxation out of the Franck-Condon region that suggests a barrierless reaction coordinate. This fast molecular motion is shown to be accompanied by the excitation of coherent excited-state structural motion. The implications of these observations for manipulating motor efficiency are discussed.

Light‐Driven Chiral Molecular Switches or Motors in Liquid Crystals

The ability to tune molecular self-organization with an external stimulus is a main driving force in the bottom-up nanofabrication of molecular devices. Light-driven chiral molecular switches or motors in liquid crystals that are capable of self-organizing into optically tunable helical superstructures undoubtedly represent a striking example, owing to their unique property of selective light reflection and which may lead to applications in the future. In this review, we focus on different classes of light-driven chiral molecular switches or motors in liquid crystal media for the induction and manipulation of photoresponsive cholesteric liquid crystal systems and their consequent applications. Moreover, the change of helical twisting powers of chiral dopants and their capability of helix inversion in the induced cholesteric phases are highlighted and discussed in the light of their molecular geometric changes.

Computational Study on the Working Mechanism of a Stilbene Light-Driven Molecular Rotary Motor: Sloped Minimal Energy Path and Unidirectional Nonadiabatic Photoisomerization

The working mechanism of a geometrically overcrowded, chiral stilbene light-driven molecular rotary motor [(2R,2R)-2,2',7,7'-tetramethyl-1,1'-bis(indanylidene), 3] has been investigated by a potential energy surface (PES) study. The reaction paths of the two photoinitiated cis-trans (or E/Z) isomerization processes, namely, (P,P)-stable-cis→(M,M)-unstable-trans-3 and (P,P)-stable-trans→(M,M)-unstable-cis-3, have been explored at the CASPT2//CASSCF level of theory. The minimal energy reaction paths (MEPs) of these two processes are nearly parallel on the PESs, separated by a ridge of high inversion barrier. The MEPs have a remarkably steep slope, which drives C═C bond rotation unidirectionally. The asymmetric bias on the excited-state MEPs is caused by the substituents on the "fjord" region as well as by the phenyl moieties. The overall photoisomerization reaction can be described as a three-state (1B→2A→1A) multimode mechanism: The molecule excited to the 1B state first crosses one of the sloped 1B/2A seams, and then follows two cooperative torsional reaction modes to cross preferentially one of the two 2A/1A conical intersections to reach the isomerized ground-state product.

Theoretical Design of a Light-Driven Molecular Rotary Motor with Low Energy Helical Inversion: 9-(5-Methyl-2-phenyl-2-cyclopenten-1-ylidene)-9H-fluorene

A light-driven molecular rotary motor of 9-(5-methyl-2-phenyl-2-cyclopenten-1-ylidene)-9H-fluorene (MPCPF) has been designed by means of ab initio complete active space self-consistent field and its second order multireference Møller-Plesset perturbation methods. In the present model molecule of MPCPF, 9H-fluorene (as a stator) and 5-methyl-2-phenyl-2-cyclopenten-1-ylidene (as a rotor) are directly linked with each other by a C═C double bond. Even by a substitution of phenyl group, MPCPF comes to have a stable P-helical MPCPF and a metastable M-helical MPCPF, and exhibits unidirectionality around the C═C double bond. In addition, interchange of the helicity can proceed with a low energy barrier through a floppy phenyl torsional motion. This is in contrast to previous light-driven molecular rotary motors where the unidirectionality is ensured by rigid and sterically overcrowded rotors. In the full rotary process of MPCPF, therefore, constancy of the rotation speed is expected to be much more improved as well as unidirectionality.

Control of Rotor Function in Light-Driven Molecular Motors

A study is presented on the control of rotary motion of an appending rotor unit in a light-driven molecular motor. Two new light driven molecular motors were synthesized that contain aryl groups connected to the stereogenic centers. The aryl groups behave as bidirectional free rotors in three of the four isomers of the 360° rotation cycle, but rotation of the rotors is hindered in the fourth isomer. Kinetic studies of both motor and rotor functions of the two new compounds are given, using (1)H NMR, 2D-EXSY NMR, and UV-vis spectroscopy. In addition, we present the development of a new method for introducing a range of aryl substituents at the α-carbon of precursors for molecular motors. The present study shows how the molecular system can be photochemically switched between a state of free rotor rotation and a state of hindered rotation and reveals the dynamics of coupled rotary systems.

Periodic one-dimensional hopping model with transitions between nonadjacent states

A one-dimensional hopping model is useful for describing the motion of microscopic particles in a thermal noise environment. Recent experiments on the new generation of light-driven rotary molecular motors found that a motor in state i can jump forward to state i+1 or i+2 or backward to state i-1 or i-2 directly. In this paper, inspired by these experiments, such a modified periodic one-dimensional hopping model with arbitrary period N is studied theoretically. The mean velocity, effective diffusion constant, and mean dwell time in one single mechanochemical cycle are obtained. The corresponding results are illustrated and verified by being applied to the synthetic rotary molecular motors.

Controlling the Spatial Orientation of Molecular Actuators: Polarized Photoisomerization of 2-Nitro-9-(2,2,2-triphenylethylidene)fluorene in a Thin Polymer Matrix

The molecule 2-nitro-9-(2,2,2-triphenylethylidene)fluorene (NTEF) was studied as a potential light-driven molecular motor. Absorption at 355 nm causes a reversible spatial reorientation of the angular distribution of the dibenzofulvene rotor moiety of NTEF when immobilized in a poly(methyl methacrylate) (PMMA) matrix adsorbed on a fused silica surface in air at room temperature. The photoreorientation dynamics was probed by polarized normal incidence cavity ringdown spectroscopy (NICRDS) when the matrix was irradiated by linearly polarized "drive" light. Polarized drive irradiation at 355 nm creates a "hole" in the angular distribution of the molecular transition dipoles. Changing the polarization of the drive beam refills the hole, creating a new hole. A stochastic model was fitted to the experimental hole burning measurements to obtain a photoreorientation quantum yield (Φ(reorient) = 0.014). The photoreorientation process appears to be driven by photoisomerization of the exocyclic dibenzofulvene double bond of NTEF.

Adhesion of Photon-Driven Molecular Motors to Surfaces via 1,3-Dipolar Cycloadditions: Effect of Interfacial Interactions on Molecular Motion

We report the attachment of altitudinal light-driven molecular motors to surfaces using 1,3-dipolar cycloaddition reactions. Molecular motors were designed containing azide or alkyne groups for attachment to alkyne- or azide-modified surfaces. Surface attachment was characterized by UV-vis, IR, XPS, and ellipsometry measurements. Surface-bound motors were found to undergo photochemical and thermal isomerizations consistent with unidirectional rotation in solution. Confinement at a surface was found to reduce the rate of the thermal isomerization process. The rate of thermal isomerization was also dependent on the surface coverage of the motors. In solution, changes in the UV-vis signal that accompany thermal isomerization can be fit with a single monoexponential decay. In contrast, thermal isomerization of the surface-bound motors does not follow a single monoexponential decay and was found to fit a biexponential decay. Both one- and two-legged motors were attached to surfaces. The kinetics of thermal isomerization was not affected by the valency of attachment, indicating that the changes in kinetics from solution to surface systems are related to interactions between the surface-bound motors.

Reversing the direction in a light-driven rotary molecular motor

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.

Rotary Molecular Motors: A Large Increase in Speed through a Small Change in Design

Reducing the steric interaction between the upper-half and the lower-half of a light-driven rotary molecular motor by decreasing the size of the aromatic moiety in the upper-half from a naphthalene to a benzothiophene results in an almost 3500 times faster rotation.

Understanding the Dynamics Behind the Photoisomerization of a Light-Driven Fluorene Molecular Rotary Motor

Light-driven molecular rotary motors derived from chiral overcrowded alkenes represent a broad class of compounds for which photochemical rearrangements lead to large scale motion of one part of the molecule with respect to another. It is this motion/change in molecular shape that is employed in many of their applications. A key group in this class are the molecular rotary motors that undergo unidirectional light-driven rotation about a double bond through a series of photochemical and thermal steps. In the present contribution we report a combined quantum chemical and molecular dynamics study of the mechanism of the rotational cycle of the fluorene-based molecular rotary motor 9-(2,4,7-trimethyl-2,3-dihydro-1H-inden-1-ylidene)-9H-fluorene (1). The potential energy surfaces of the ground and excited singlet states of 1 were calculated, and it was found that conical intersections play a central role in the mechanism of photo conversion between the stable conformer of 1 and its metastable conformer. Molecular dynamics simulations indicate that the average lifetime of the fluorene motor in the excited state is 1.40 +/- 0.10 ps when starting from the stable conformer, which increases to 1.77 +/- 0.13 ps for the reverse photoisomerization. These simulations indicate that the quantum yield of photoisomerization of the stable conformer is 0.92, whereas it is only 0.40 for the reverse photoisomerization. For the first time, a theoretical understanding of the experimentally observed photostationary state of 1 is reported that provides a detailed picture of the photoisomerization dynamics in overcrowded alkene-based molecular motor 1. The analysis of the electronic structure of the fluorene molecular motor holds considerable implications for the design of molecular motors. Importantly, the role of pyramidalization and conical intersections offer new insight into the factors that dominate the photostationary state achieved in these systems.