Fine tuning of molecular rotor function in photochemical molecular switches

Molecular switches are used as scaffolds for the construction of controlled molecular rotors. The internal position of the switching entity in the molecule controls the dynamic behaviour of the rotor moiety in the molecule. Six new molecular motors with o-xylyl rotor moieties were prepared on the basis of an overcrowded alkene, and their dynamics were systematically studied by 2D EXSY NMR. Variation of the (hetero-)atoms in the upper and lower halves of the overcrowded alkene allows fine tuning of the rate of rotation of the o-xylyl rotor in the lower half of the molecule. For all rotors it was observed that the rotation barrier for the trans-isomer was higher than that of the corresponding cis-isomer. The results are analyzed and discussed in terms of differences in steric interactions in the presented system.     

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 M?ller-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.     

Direct Observation of Hemithioindigo‐Motor Unidirectionality

Hemithioindigo molecular motors undergo very fast unidirectional rotation upon irradiation with visible light, which has prevented a complete analysis of their working mechanism. In this work, we have considerably slowed down their motion by using a new synthesis for sterically hindered motor derivatives. This method allowed the first observation of all four intermediate states populated during rotation. The exact order in which each isomeric state is formed under irradiation conditions was elucidated using low temperature ¹H NMR spectroscopy in conjunction with other analytical methods. At the same time, complete unidirectionality could also be directly shown. Access to slowly rotating hemithioindigo motors opens up a plethora of new applications for visible‐light‐induced unidirectional motions, especially in areas such as catalysis, smart materials, and supramolecular chemistry.     

Guest-accelerated molecular rotor

A molecular rotor was designed in which the rate of rotation is accelerated by guest complexation. The binding of an acetate guest to the urea groups lowers the barrier of the adjacent C(aryl)-N(imide) bond by 2 to 4 kcal/mol. This behavior is in contrast to most molecular rotors in which guest complexation slows rotation.     

Exploring the boundaries of a light-driven molecular motor design: new sterically overcrowded alkenes with preferred direction of rotation

Insight in the steric and electronic parameters governing isomerization processes in artificial molecular motors is essential in order to design more advanced motor systems. A subtle balance of steric parameters and the combination of helical and central chirality are key features of light-driven unidirectional rotary molecular motors constructed so far. In an approach to decrease the steric hindrance around the central olefinic bond (rotary axis) and thereby lowering the energy barrier for helix inversion resulting in an increased rotation rate, the boundaries of our molecular motor design are explored. In a new design of a light-driven molecular motor based on a sterically overcrowded alkene the methyl substituent adjacent to the stereogenic center, which is responsible for the control of the direction of rotation, is shifted one position away from the fjord region of the molecule compared to the second-generation motor systems. In contrast to previously developed light-driven molecular motors, there is a preference for the methyl substituent to adopt a pseudo-equatorial orientation. Nevertheless, this new type of motor is capable of functioning as a rotary molecular motor, albeit not with full unidirectionality. Under the combined influence of light and heat, there is a preferred clockwise rotation of one half of the molecule. Surprisingly, the effect of shifting the methyl substituent on the energy barrier for helix inversion is small and even a slight increase in the barrier is observed.     

Design of a molecular memory element with an alternating circular array of dipolar rotors and rotation suppressors

As a new element for electric-field driven molecular memory, we developed a hexaarylbenzene derivative in which three difluorophenyl groups and three aryl groups as a dipolar rotor and a rotation suppressor, respectively, are alternately positioned on the central benzene core. This molecule has two rotational isomeric forms, both of which preserve their conformational states at room temperature but exhibit interconversion at high temperatures. Amorphous thin films fabricated from the hexaarylbenzene show a reversible change in surface potential by application of electric fields.

A hexaarylbenzene derivative with an alternating circular array of dipolar rotors and rotation suppressors holds promise as a new element for electric-field driven molecular memory.     

Giant Crystalline Molecular Rotors that Operate in the Solid State

Molecular motion in the solid state is typically precluded by the highly dense environment, and only molecules with a limited range of sizes show such dynamics. Here, we demonstrate the solid-state rotational motion of two giant molecules, i.e., triptycene and pentiptycene, by encapsulating a bulky N-heterocyclic carbene (NHC) Au(I) complex in the crystalline media. To date, triptycene is the largest molecule (surface area: 245 Ų; volume: 219 ų) for which rotation has been reported in the solid state, with the largest rotational diameter among reported solid-state molecular rotors (9.5 Å). However, the pentiptycene rotator that is the subject of this study (surface area: 392 Ų; volume: 361 ų; rotational diameter: 13.0 Å) surpasses this record. Single-crystal X-ray diffraction analyses of both the developed rotors revealed that these possess sufficient free volume around the rotator. The molecular motion in the solid state was confirmed using variable-temperature solid-state ²H spin-echo NMR studies. The triptycene rotor exhibited three-fold rotation, while temperature-dependent changes of the rotational angle were observed for the pentiptycene rotor.     

Molecular compasses and gyroscopes. II. Synthesis and characterization of molecular rotors with axially substituted bis[2-(9-triptycyl)ethynyl]arenes

We have developed a simple convergent procedure for the synthesis of molecular rotors consisting of a central aromatic group coupled with two axially positioned ethynyltriptycenes. Molecular rotors with 1,4-phenylene (1), 1,4'-1,1'-biphenylene (2), 9,10-anthracenylene (3), and 2,7-pyrenylene (4) groups were prepared by Pd(0)-catalyzed coupling of ethynyl triptycenes with the corresponding dibromoarenes. Although compounds 1-4 were not expected to have free rotation in the solid state, the rotational potentials of 1 and 3 were analyzed by semiempirical methods and the crystal packing of 1 was analyzed to design the structures most likely to yield a functional rotor in the solid state. Semiempirical PM3 calculations predict compounds 1, 2, and 4 to have frictionless internal rotation even at temperatures as low as 25 K, while compound 3 is expected to have a barrier of ca. 4 kcal/mol.     

Enantiopure Functional Molecular Motors Obtained by a Switchable Chiral‐Resolution Process

Molecular switches, rotors, and motors play an important role in the development of nano‐machines and devices, as well as responsive and adaptive functional materials. For unidirectional rotors based on chiral overcrowded alkenes, their stereochemical homogeneity is of crucial importance. Herein, a method to obtain new and functionalizable overcrowded alkenes in enantiopure form is presented. The procedure involves a short synthesis of three steps and a solvent‐switchable chiral resolution by using a readily available resolving agent. X‐ray crystallography revealed the mode of binding of the motor with the resolving agent, as well as the absolute configuration of the motor. ¹H NMR and UV/Vis spectroscopy techniques were used to determine the dynamic behavior of this molecular motor. This method provides rapid access to ample amounts of enantiopure molecular motors, which will greatly facilitate the further development of responsive molecular systems based on chiral overcrowded alkenes.     

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.

Various families of light-driven rotary molecular motors and the key aspects of motor design are discussed. Comparisons are made between the strengths and weaknesses of each motor. Challenges, applications, and future prospects are explored.     

Nanoporous Films with Oriented Arrays of Molecular Motors for Photoswitching the Guest Adsorption and Diffusion

Molecular motors are fascinating nanomachines. However, constructing smart materials from such functional molecules presents a severe challenge in material science. Here, we present a bottom-up layer-by-layer assembly of oriented overcrowded-alkene molecular motors forming a crystalline metal–organic framework thin film. While all stator parts of the overcrowded-alkene motors are oriented perpendicular to the substrate, the rotors point into the pores, which are large enough allowing for the light-induced molecular rotation. Taking advantage of the thin film's transparency, the motor rotation and its activation energy are determined by UV/Vis spectroscopy. As shown by gravimetric uptake experiments, molecular motors in crystalline porous materials are used, for the first time, to control the adsorption and diffusion properties of guest molecules in the pores, here, by switching with light between the (meta-)stable states. The work demonstrates the potential of designed materials with molecular motors and indicates a path for the future development of smart materials.     

Tuning the Ground and Excited State Dynamics of Hemithioindigo Molecular Motors by Changing Substituents

Efficiency and performance of light triggered molecular motors are crucial features that need to be mechanistically understood to improve the performance and enable conscious property tailoring for specific applications. In this work, three different hemithioindigo-based molecular motors are investigated and all four steps in their complete unidirectional rotation are unraveled fully quantitatively. Transient absorption spectroscopy across twelve orders of magnitude in time is used to probe the fs nuclear motions up to the ms thermal kinetics, covering the timeframe of the whole motor rotation. The newly known full mechanisms allow simulation of the motor systems to scrutinize their performance at realistic illumination conditions. This highlights the importance of photoisomerization quantum yields for the rotation speed. The substitution pattern in close proximity to the rotation axle influences the excited and ground state properties. Reduction of electron donation and concomitant increase of steric hindrance leads to faster photoisomerization reactions with quasi-ballistic behavior, but also to a slight decrease in the quantum efficiency. The expected decelerating effects of increased sterics are primarily manifested in the ground state. A promising approach for next-generation hemithioindigo motors is to elevate electron donation at the rotor fragment followed by an increase of steric hindrance.     

Crankshaft motion in a highly congested bis(triarylmethyl)peroxide

Crankshaft motion has been proposed in the solid state for molecular fragments consisting of three or more rotors linked by single bonds, whereby the two terminal rotors are static and the internal rotors experience circular motion. Bis-[tri-(3,5-di-tert-butyl)phenylmethyl]-peroxide 2 was tested as a model in search of crankshaft motion at the molecular level. In the case of peroxide 2, the bulky trityl groups may be viewed as the external static rotors, while the two peroxide oxygens can undergo the sought after internal rotation. Evidence for this process in the case of peroxide 2 was obtained from conformational dynamics determined by variable-temperature (13)C and (1)H NMR between 190 and 375 K in toluene-d(8). Detailed spectral assignments for the interpretation of two coalescence processes were based on a correlation between NMR spectra obtained in solution at low temperature, in the solid state by (13)C CPMAS NMR, and by GIAO calculations based on a B3LYP/6-31G structure of 2 obtained from its X-ray coordinates as the input. Evidence supporting crankshaft rotation rather than slippage of the trityl groups was obtained from molecular mechanics calculations.     

Increased speed of rotation for the smallest light-driven molecular motor

In this paper we present the smallest artificial light-driven molecular motor consisting of only 28 carbon and 24 hydrogen atoms. The concept of controlling directionality of rotary movement at the molecular level by introduction of a stereogenic center next to the central olefinic bond of a sterically overcrowded alkene does not only hold for molecular motors with six-membered rings, but is also applicable to achieve the unidirectional movement for molecular motors having five-membered rings. Although X-ray analyses show that the five-membered rings in the cis- and trans-isomer of the new molecular motor are nearly flat, the energy differences between the (pseudo-)diaxial and (pseudo-)diequatorial conformations of the methyl substituents in both isomers are still large enough to direct the rotation of one-half of the molecule with respect to the other half in a clockwise fashion. The full rotary cycle comprises four consecutive steps: two photochemical isomerizations each followed by a thermal helix inversion. Both photochemical cis-trans isomerizations proceed with a preference for the unstable diequatorial isomers over the stable diaxial isomers. The thermal barriers for helix inversion of this motor molecule have decreased dramatically compared to its six-membered ring analogue, the half-life of the fastest step being only 18 s at room temperature.     

The 1-D hindered rotor approximation

We offer an overview of the popular one- dimensional (1-D) hindered rotor model that is often used for quantum mechanical treatment of internal rotation. This model is put in context with other methods used for treating anharmonic motions. The 1-D hindered rotor scheme is general for tops of any symmetry and has been used to provide accurate treatment of hindered rotors in a wide range of systems. One obstacle preventing wider use of the model is its lack of incorporation into common electronic structure codes. We have developed an algorithm for consistently treating all tops in a molecule, and we present simple codes which interface with electronic structure codes to provide thermochemical properties (S, C _p , H) of individual species and reactions that have been corrected for internal rotations. Finally, we use this approach to give sensible advice about how the model can be used best. We show that dramatic changes in the reduced moment of inertia do not necessarily cause comparable changes in the properties of individual hindered rotors. We demonstrate that the rotational hindrance potential can be accurately determined using relatively coarse step sizes. Finally, we show that internal rotation in transition states can be treated using a “frozen transition state” approximation at a significant computational savings. We also discuss the relationship between calculated properties of hindered rotors and the choice of method and basis set used. Electronic Supplementary Material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Inside Cover: Bending Actuation of Hydrogels through Rotation of Light-Driven Molecular Motors (Angew. Chem. Int. Ed. 13/2023)

The unidirectional rotation of chemically crosslinked light-driven molecular motors is shown to progressively shift the swelling equilibrium of hydrogels. The concentration of molecular motors and the initial strand density of the polymer network are key parameters to modulate the macroscopic contraction of the material, and both parameters can be tuned using polymer chains of different molecular weights. These findings led to the design of optimized hydrogels revealing a half-time contraction of approximately 5 min. Furthermore, under inhomogeneous stimulation, the local contraction event was exploited to design useful bending actuators with an energy output 400 times higher than for previously reported self-assembled systems involving rotary motors. In the present configuration, we measure that a single molecular motor can lift up loads of 200 times its own molecular weight.     

Towards Dynamic Control of Wettability by Using Functionalized Altitudinal Molecular Motors on Solid Surfaces

We report the synthesis of altitudinal molecular motors that contain functional groups in their rotor part. In an approach to achieve dynamic control over the properties of solid surfaces, a hydrophobic perfluorobutyl chain and a relatively hydrophilic cyano group were introduced to the rotor part of the motors. Molecular motors were attached to quartz surfaces by using interfacial 1,3‐dipolar cycloadditions. To test the effect of the functional groups on the rotary motion, photochemical and thermal isomerization studies of the motors were performed both in solution and when attached to the surface. We found that the substituents have no significant effect on the thermal and photochemical processes, and the functionalized motors preserved their rotary function both in solution and on a quartz surface. Preliminary results on the influence of the functional groups on surface wettability are also described.     

Theory of damped quantum rotation in NMR spectra. I. Fundamental aspects

The damped quantum rotation (DQR) theory, formulated originally for methyl-like atomic groupings, is now extended to hindered (N>3)-fold molecular rotors, such as the cyclopentadienyl, benzene, and cycloheptatrienyl rings in solid phase environments. It heightens the significance of the Pauli principle in shaping up the stochastic dynamics of such objects, reflected in NMR line shapes. The corresponding NMR line-shape equation is derived; its stochastic part is shown for the first time to have the double commutator form for any values of the quantum-mechanical (coherence-damping) rate constants entering it. Constraints on the relative magnitudes of such constants are determined under which the DQR line-shape equation is converted into the phenomenological Alexander-Binsch equation describing classical jumps of the rotor. When all the quantum rate constants happen to be equal, the phenomenological model of equal jump rates between any two of the N (equivalent) orientations of the rotor is reproduced. On the other hand, the seemingly most plausible (for N>3) nearest-neighbor hopping model does not have any peculiar grounds in the DQR approach. For the special instances of stochastic molecular motions addressed in this work, the extended DQR formalism affords a quantification of the "degree of classicality" represented by a complete set of the relevant quantum rate constants. In view of our earlier experimental findings for the methyl rotors, the very occurrence of the nonclassical DQR effects seems unquestionable even for the objects of the size of benzene. The question of under what circumstances such effects can be big enough to be detected experimentally will be addressed in Part II of this work.     

Electron-triggered motions in technomimetic molecules

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 technomimetic molecules with motions triggered by electrons. The first part is devoted to our work in the field of molecular switches: after having demonstrated the possibility of controlling an intramolecular electron transfer by photoisomerisation, we are now trying to control the isomerisation, either by electrochemistry, or by embedding the photochromic compound in a self-assembled monolayer and testing the electrical conduction with a STM tip. In a second part, we present our strategy on controlling the rotation in a molecular rotary motor and the family of ruthenium complexes designed to perform such a task. The molecules have a piano-stool structure with a "stator" meant to be grafted on an oxide surface, and a "rotor" bearing redox-active groups, so that addressing the molecule with nano-electrodes would trigger rotation. The electrical control of the charge state of a molecule by a STM tip is developed in a final part.