Light-driven Rotary Molecular Motors Research Articles

All-visible-light-driven salicylidene schiff-base-functionalized artificial molecular motors

Light-driven rotary molecular motors are among the most promising classes of responsive molecular machines and take advantage of their intrinsic chirality which governs unidirectional rotation. As a consequence of their dynamic function, they receive considerable interest in the areas of supramolecular chemistry, asymmetric catalysis and responsive materials. Among the emerging classes of responsive photochromic molecules, multistate first-generation molecular motors driven by benign visible light remain unexplored, which limits the exploitation of the full potential of these mechanical light-powered systems. Herein, we describe a series of all-visible-light-driven first-generation molecular motors based on the salicylidene Schiff base functionality. Remarkable redshifts up to 100 nm in absorption are achieved compared to conventional first-generation motor structures. Taking advantage of all-visible-light-driven multistate motor scaffolds, adaptive behaviour is found as well, and potential application in multistate photoluminescence is demonstrated. These functional visible-light-responsive motors will likely stimulate the design and synthesis of more sophisticated nanomachinery with a myriad of future applications in powering dynamic systems.

Motorized Photomodulator: Making A Non-photoresponsive Supramolecular Gel Switchable by Light.

Introducing photo-responsive molecules offers an attractive approach for remote and selective control and dynamic manipulation of material properties. However, it remains highly challenging how to use a minimal amount of photo-responsive units to optically modulate materials that are inherently inert to light irradiation. Here we show the application of a light-driven rotary molecular motor as a "motorized photo-modulator" to endow a typical H-bond-based gel system with the ability to respond to light irradiation and create a reversible sol-gel transition. The key molecular design feature is the introduction of a minimal amount (2 mol %) of molecular motors into the supramolecular network as photo-switchable non-covalent crosslinkers. Advantage is taken of the subtle interplay of the large geometry change during photo-isomerization of the molecular motor guest and the dynamic nature of a supramolecular gel host system. As a result, a tiny amount of molecular motors is enough to switch the mechanical modulus of the entire supramolecular systems. This study proves the concept of designing photo-responsive materials with minimum use of non-covalent light-absorbing units.

Simultaneously improving the efficiencies of photo- and thermal isomerization of an oxindole-based light-driven molecular rotary motor by a structural redesign.

We designed a novel highly efficient light-driven molecular rotary motor theoretically by using electronic structure calculations and nonadiabatic dynamics simulations, and it showed excellent performance for both photo- and thermal isomerization processes simultaneously. By the small structural modification based on 3-(2,7-dimethyl-2,3-dihydro-1H-inden-1-ylidene)-1-methylindolin-2-one (DDIYM) synthesized by Feringa et al. recently, an oxindole-based light-driven molecular rotary motor, 3-(1,5-dimethyl-4,5-dihydrocyclopenta[b]pyrrol-6(1H)-ylidene)-1-methylindolin-2-one (DDPYM), is proposed, which displays a significant electronic push-pull character and weak steric hindrance for double-bond isomerization. The newly designed motor DDPYM shows a remarkable improvement of the quantum yield for both EP → ZM and ZP → EM photoisomerization processes, compared to the original motor DDIYM. Furthermore, the rotary motion in photoisomerization processes of DDPYM behaves more like a pure axial rotational motion approximately, while that of DDIYM is an obvious precessional motion. The weakness of the steric hindrance reduces the energy barriers of the thermal helix EM → EP and ZM → ZP inversion steps, and would accelerate two ground-state isomerization steps significantly. Our results confirm the feasibility of simultaneously improving the efficiencies of photo- and thermal isomerization of oxindole-based light-driven molecular rotary motors and this design idea sheds light on the future development of more efficient molecular motors.

Coupled Rocking Motion in a Light-Driven Rotary Molecular Motor.

Coupled motion is ubiquitous in Nature as it forms the base for the direction, amplification, propagation, and synchronization of movement. Herein, we present experimental proof for the coupling of the rocking motion of a dihydroanthracene stator moiety with the light-induced rotational movement of an overcrowded alkene-based molecular motor. The motor was desymmetrized, introducing two different alkyl substituents to the stator part of the molecular scaffold, resulting in the formation of two diastereomers with opposite axial chirality. The structure of the two isomers is determined with nuclear Overhauser effect spectroscopy NMR and single-crystal X-ray analysis. The desymmetrization enables the study of the coupled motion, that is, rotation and oscillation, by 1H NMR, findings that are further supported by density functional theory calculations. A new handle to regulate the rotational speed of the motor through functionalization in the bottom half was also introduced, as the thermal barrier for thermal helix inversion is found to be largely dependent on the alkyl substituents and its orientation toward the upper half of the motor scaffold. In addition to the commonly observed successive photochemical and thermal steps driving the rotation of the motor, we find that the motor undergoes photochemically driven rotation in three of the four steps of the rotation cycle. Hence, this result extends the scope of molecular motors capable of photon-only rotary behavior.

Synergistic interplay between photoisomerization and photoluminescence in a light-driven rotary molecular motor

Photoactuators and photoluminescent dyes utilize light to perform mechanical motion and undergo spontaneous radiation emission, respectively. Combining these two functionalities in a single molecule would benefit the construction of advanced molecular machines. Due to the possible detrimental interaction between the two light-dependent functional parts, the design of hybrid systems featuring both functions in parallel remains highly challenging. Here, we develop a light-driven rotary molecular motor with an efficient photoluminescent dye chemically attached to the motor, not compromising its motor function. This molecular system shows efficient rotary motion and bright photoluminescence, and these functions can be addressed by a proper choice of excitation wavelengths and solvents. The moderate interaction between the two parts generates synergistic effects, which are beneficial for lower-energy excitation and chirality transfer from the motor to the photoluminescent dye. Our results provide prospects towards photoactive multifunctional systems capable of carrying out molecular rotary motion and tracking its location in a complex environment.

Effect of Temperature on Photoisomerization Dynamics of a Newly Designed Two-Stroke Light-Driven Molecular Rotary Motor.

The working mechanism of conventional light-driven molecular rotary motors, especially Feringa-type motors, contains two photoisomerization steps and two thermal helix inversion steps. Due to the existence of a thermal helix inversion step, both the ability to work at lower temperatures and the rotation speed are limited. In this work, a two-stroke light-driven molecular rotary motor, 2-(1,5-dimethyl-4,5-dihydrocyclopenta[b]pyrrol-6(1H)-ylidene)-1,2-dihydro-3H-pyrrol-3-one (DDPY), is proposed, which is capable of performing unidirectional and repetitive rotation by only two photoisomerization (EP→ZP and ZP→EP) steps. With trajectory surface-hopping simulation at the semi-empirical OM2/MRCI level, the EP→ZP and ZP→EP nonadiabatic dynamics of DDPY were systematically studied at different temperatures. Both EP→ZP and ZP→EP photoisomerizations are on an ultrafast timescale (ca. 200–300 fs). The decay mode of EP→ZP photoisomerization is approximately bi-exponential, while that of ZP→EP photoisomerization is found to be periodic. For EP and ZP isomers of DDPY, after the S→S excitation, the dynamical processes of nonadiabatic decay are both followed by twisting about the central C=C double bond and the pyramidalization of the C atom at the stator-axle linkage. The effect of temperature on the nonadiabatic dynamics of EP→ZP and ZP→EP photoisomerizations of DDPY has been systematically investigated. The average lifetimes of the S excited state and quantum yields for both EP→ZP and ZP→EP photoisomerization are almost temperature-independent, while the corresponding unidirectionality of rotation is significantly increased (e.g., 74% for EP→ZP and 72% for ZP→EP at 300 K vs 100% for EP→ZP and 94% for ZP→EP at 50 K) with lowering the temperature.

Design and Nonadiabatic Photoisomerization Dynamics Study of a Three-Stroke Light-Driven Molecular Rotary Motor.

Working cycle of conventional light-driven molecular rotary motors (LDMRMs), especially Feringa-type motors, usually have four steps, two photoisomerization steps, and two thermal helix inversion (THI) steps. THI steps hinder the ability of the motor to operate at lower temperatures and limit the rotation speed of LDMRMs. A three-stroke LDMRM, 2-(2,7-dimethyl-2,3-dihydro-1H-inden-1-ylidene)-1,2-dihydro-3H-pyrrol-3-one (DDIY), is proposed, which is capable of completing an unidirectional rotation by two photoisomerization steps and one thermal helix inversion step at room temperature. On the basis of trajectory surface-hopping simulation at the semi-empirical OM2/MRCI level, the EP→ZP and ZP→EM nonadiabatic photoisomerization dynamics of DDIY were systematically analyzed. Quantum yields of EP→ZP and ZP→EM photoisomerization of DDIY are ca. 34% and 18%, respectively. Both EP→ZP and ZP→EM photoisomerization processes occur on an ultrafast time scale (ca. 100–300 fs). This three-stroke LDMRM may stimulate further research for the development of new families of more efficient LDMRMs.

Controlling rotary motion of molecular motors based on oxindole.

Molecular motors are essential components of artificial molecular machines, which can be used to manipulate and amplify mechanical motion at the nanoscale to create machine-like function. Since the discovery of light-driven rotary molecular motors, the field has been widely developed, including the introduction of molecular motors based on oxindole by our group in 2019. The rotational properties of molecular motors, e.g. absorption wavelength, quantum yield and rotation speed, often critically depend on substituent effects. Up to now, the substituent effects of oxindole-based molecular motors have not yet been investigated. Herein, we present a family of oxindole-based molecular motors functionalised at three different positions on the motor core, with either CN or OMe groups. The motors prepared in this work retain the favourable features of oxindole-based motors, i.e. simple synthesis and visible light addressability. We find that functionalisation has substantial effects on the absorption wavelength of the motors, meanwhile the rotation speed is unaffected. Furthermore, we found that functionalisation of the oxindole molecular motors increases their quantum efficiency considerably in comparison to previous motors of their class.

Photophysics of First-Generation Photomolecular Motors: Resolving Roles of Temperature, Friction, and Medium Polarity.

Light-driven unidirectional molecular rotary motors have the potential to power molecular machines. Consequently, optimizing their speed and efficiency is an important objective. Here, we investigate factors controlling the photochemical yield of the prototypical unidirectional rotary motor, a sterically overcrowded alkene, through detailed investigation of its excited-state dynamics. An isoviscosity analysis of the ultrafast fluorescence decay data resolves friction from barrier effects and reveals a 3.4 ± 0.5 kJ mol-1 barrier to excited-state decay in nonpolar media. Extension of this analysis to polar solvents shows that this barrier height is a strong function of medium polarity and that the decay pathway becomes near barrierless in more polar media. Thus, the properties of the medium can be used as a route for controlling the motor's excited-state dynamics. The connection between these dynamics and the quantum yield of photochemical isomerization is probed. The photochemical quantum yield is shown to be a much weaker function of solvent polarity, and the most efficient excited-state decay pathway does not lead to a strongly enhanced quantum yield for isomerization. These results are discussed in terms of the solvent dependence of the complex multidimensional excited-state reaction coordinate.

Theoretical investigation of a novel xylene-based light-driven unidirectional molecular motor.

In this study, the working mechanism of the first light-driven rotary molecular motors used to control an eight-base-pair DNA hairpin has been investigated. In particular, this linker was reported to have promising photophysical properties under physiological conditions, which motivated our work at the quantum mechanical level. Cis-trans isomerization is triggered by photon absorption at wavelengths ranging 300 nm-400 nm, promoting the rotor to the first excited state, and it is mediated by an energy-accessible conical intersection from which the ground state is reached back. The interconversion between the resulting unstable isomer and its stable form occurs at physiological conditions in the ground state and is thermally activated. Here, we compare three theoretical frameworks, generally used in the quantum description of medium-size chemical systems: Linear-Response Time-Dependent Density Functional Theory (LR-TDDFT), Spin-Flip TDDFT (SF-TDDFT), and multistate complete active space second-order perturbation theory on state-averaged complete active space self consistent field wavefunctions (MS-CASPT2//SA-CASSCF). In particular, we show the importance of resorting to a multireference approach to study the rotational cycle of light-driven molecular motors due to the occurrence of geometries described by several configurations. We also assess the accuracy and computational cost of the SF-TDDFT method when compared to MS-CASPT2 and LR-TDDFT.

Designing light-driven rotary molecular motors.

The ability to induce and amplify motion at the molecular scale has seen tremendous progress ranging from simple molecular rotors to responsive materials. In the two decades since the discovery of light-driven rotary molecular motors, the development of these molecules has been extensive; moving from the realm of molecular chemistry to integration into dynamic molecular systems. They have been identified as actuators holding great potential to precisely control the dynamics of nanoscale devices, but integrating molecular motors effectively into evermore complex artificial molecular machinery is not trivial. Maximising efficiency without compromising function requires conscious and judicious selection of the structures used. In this perspective, we focus on the key aspects of motor design and discuss how to manipulate these properties without impeding motor integrity. Herein, we describe these principles in the context of molecular rotary motors featuring a central double bond axle and emphasise the strengths and weaknesses of each design, providing a comprehensive evaluation of all artificial light-driven rotary motor scaffolds currently present in the literature. Based on this discussion, we will explore the trajectory of research into the field of molecular motors in the coming years, including challenges to be addressed, potential applications, and future prospects.

A Chemically Driven Rotary Molecular Motor Based on Reversible Lactone Formation with Perfect Unidirectionality

Summary Among the amazing variety of ingenious molecular machines present in living organisms, enabling motility, responsiveness, and out-of-equilibrium behavior among others, rotary motors, such as the ATPase and bacterial flagellar motors, hold a special position. While these biological machines are mainly powered by chemical conversion and artificial light-driven rotary molecular motors have been well established, genuine chemically driven rotary motor systems are very limited. Here, we report a chemically powered rotary molecular motor based on biaryl structures that allows complete 360° unidirectional rotation i.e., >99% based on simple esterification chemistry. All the stereoisomers involved in the 4-stage rotary process have been characterized using X-ray crystallography confirming the relative stereochemistry of each isomer in accordance with the sequential and complete stereoselective operation of the rotary system. Having established the basic principles of this novel molecular rotary motor, it will facilitate the design of more sophisticated future artificial machine systems driven solely by chemical energy.

Nonadiabatic Molecular Dynamics on Graphics Processing Units: Performance and Application to Rotary Molecular Motors.

Nonadiabatic molecular dynamics (NAMD) simulations of molecular systems require the efficient evaluation of excited-state properties, such as energies, gradients, and nonadiabatic coupling vectors. Here, we investigate the use of graphics processing units (GPUs) in addition to central processing units (CPUs) to efficiently calculate these properties at the time-dependent density functional theory (TDDFT) level of theory. Our implementation in the FermiONs++ program package uses the J-engine and a preselective screening procedure for the calculation of Coulomb and exchange kernels, respectively. We observe good speed-ups for small and large molecular systems (comparable to those observed in ground-state calculations) and reduced (down to sublinear) scaling behavior with respect to the system size (depending on the spatial locality of the investigated excitation). As a first illustrative application, we present efficient NAMD simulations of a series of newly designed light-driven rotary molecular motors and compare their S1 lifetimes. Although all four rotors show different S1 excitation energies, their ability to rotate upon excitation is conserved, making the series an interesting starting point for rotary molecular motors with tunable excitation energies.

Exploring the Mechanism of a Chiral N-Alkyl Imine-Based Light-Driven Molecular Rotary Motor at MS-CASPT2//CASSCF and MS-CASPT2//(TD) DFT Levels.

The working mechanism including the photoisomerization and thermal isomerization steps of a chiral N-alkyl imine-based motor synthesized by Lehn et al. are revealed by MS-CASPT2//CASSCF and MS-CASPT2//(TD-)DFT methods. For the photoisomerization process of the imine-based motor, it involves both the bright (π,π*) state and the dark (n,π*) state. In addition, the MECI has similar geometry and energy to the minimum of the S1 state, which shows that the process is barrierless and keeps the unidirectionality of rotation well; the result confirms the imine-based motor is a good candidate for a light-driven molecular rotary motor. For the thermal isomerization process of the imine-based motor, there are two even isomerization paths: one with the mechanism of the in-plane N inversion, the energy barriers of which are 29.6 kcal mol-1 at MS3-CASPT2//CAM-B3LYP level and 29.2 kcal mol-1 at MS3-CASPT2//CASSCF level; the other with the mechanism of ring inversion of the cycloheptatriene moiety, with energy barriers of 28.1 kcal mol-1 at MS3-CASPT2//CAM-B3LYP level and 18.1 kcal mol-1 at MS3-CASPT2//CASSCF level. According to the structural feature of the stator moiety, the imine molecule can be used as a two-step or a four-step light-driven rotary motor.

Molecular motors with high quantum efficiency and visible-light responsiveness: Meeting two challenges in one design

The development of light-driven rotary molecular motors is guided by a number of key goals regarding performance and applicability. While a variety of approaches to achieve high quantum yields for small UV-driven motors have been discovered, such as incorporating a protonated or alkylated nitrogen Schiff base, less progress has been made toward the goal to power molecular motors with nondestructive visible light, which will facilitate their future usage in radiation-sensitive environments. Here, we present non-adiabatic molecular dynamics simulations based on multiconfigurational quantum chemistry to demonstrate that Schiff-base motors can maintain high quantum yields also when their conjugated systems are sufficiently large for them to rather be driven by visible light. In particular, we show that a visible-light responsive Schiff-base motor featuring dihydropyridinium and cyclopentenylidene motifs achieves quantum yields of almost 70% for each of the two photoisomerizations that underlie its rotary motion.

Molecular Motors in Aqueous Environment.

Molecular motors are Nature’s solution for (supra)molecular transport and muscle functioning and are involved in most forms of directional motion at the cellular level. Their synthetic counterparts have also found a myriad of applications, ranging from molecular machines and smart materials to catalysis and anion transport. Although light-driven rotary molecular motors are likely to be suitable for use in an artificial cell, as well as in bionanotechnology, thus far they are not readily applied under physiological conditions. This results mainly from their inherently aromatic core structure, which makes them insoluble in aqueous solution. Here, the study of the dynamic behavior of these motors in biologically relevant media is described. Two molecular motors were equipped with solubilizing substituents and studied in aqueous solutions. Additionally, the behavior of a previously reported molecular motor was studied in micelles, as a model system for the biologically relevant confined environment. Design principles were established for molecular motors in these media, and insights are given into pH-dependent behavior. The work presented herein may provide a basis for the application of the remarkable properties of molecular motors in more advanced biohybrid systems.

Fulgides as Light-Driven Molecular Rotary Motors: Computational Design of a Prototype Compound.

A new family of light-driven molecular rotary motors utilizing the fulgide motif is proposed and its prototype molecule is studied by quantum chemical calculations and nonadiabatic molecular dynamics simulations. The new motor performs pure unidirectional axial rotation of the rotor blade with high quantum efficiency (ϕ ∼ 0.55-0.68) and ultrafast dynamics (⟨ t⟩ S1 ∼ 200-300 fs) of its successive photoisomerization steps. The photocyclization reaction typical of fulgide compounds is blocked by the design of the new motor and never occurred in the molecular dynamics simulations. The new motors can be synthesized from easily available precursors. In view of its remarkable photoisomerization ability, the new motor represents a prospective class of compounds for the use in nanosized molecular devices.

Toward Fast and Efficient Visible-Light-Driven Molecular Motors: A Minimal Design.

A key goal in the development of light‐driven rotary molecular motors is to facilitate their usage in biology and medicine by shifting the required irradiation wavelengths from the UV regime to the nondestructive visible regime. Although some progress has been made toward this goal, most available visible‐light‐driven motors either have relatively low quantum yields or require that thermal steps follow the photoisomerizations that underlie the rotary motion. Here, a minimal design for visible‐light‐driven motors without these drawbacks is presented and evaluated on the basis of state‐of‐the‐art quantum chemical calculations and molecular dynamics simulations. The design, featuring dihydropyridinium and cyclohexenylidene motifs and comprising only five conjugated double bonds, is found to produce a full 360° rotation through fast photoisomerizations (excited‐state lifetimes of ≈170–250 fs) powered by photons with energies well below 3 eV.

Theoretical Design and Mechanistic Study on a Light-Driven Molecular Rotary Motor with B=N Axis

Theoretical Design and Mechanistic Study on a Light-Driven Molecular Rotary Motor with B=N Axis

Excited-State Aromaticity Improves Molecular Motors: AComputational Analysis.

A new approach to the design of more efficient light-driven rotary molecular motors is presented and evaluated computationally based on molecular dynamics simulations. The approach involves enabling part of the motor to become aromatic in the photoactive excited state, and is found to sharply increase the rotary quantum yields of the photoisomerizations that underlie the motor function. Excited-state aromaticity thus holds promise as a guiding principle toward better-performing molecular motors.