Interfacing molecular photoswitches with liquid crystal polymers enables the amplification of their nanoscale motion into macroscopic shape transformations. Typically, the mechanism responsible for ...actuation involves light-induced molecular disorder. Here, we demonstrate that bistable hydrazones can drive (chiral) shape transformations in liquid crystal polymer networks, with photogenerated polymer shapes displaying a long-term stability that mirrors that of the switches. The mechanism involves a photoinduced buildup of tension in the polymer, with a negligible influence on the liquid crystalline order. Hydrazone-doped liquid crystal systems thus diversify the toolbox available to the field of light-adaptive molecular actuators and hold promise in terms of soft robotics.
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IJS, KILJ, NUK, PNG, UL, UM
Essentially, all motion in living organisms emerges from the collective action of biological molecular machines transforming chemical energy, originally harvested from light, into ordered activity. ...As a man-made counterpart to nature’s biomolecular machines, chemists have created artificial molecular machines that display controlled and even directional motion in response to light. However, to be of practical value, the motion of these light-fuelled molecular machines will have to be coupled to the rest of the world. Inspired by the complex functional movement seen in the plant and animal world, chemists have undertaken the challenge to harness molecular motion and, so, they have set artificial molecular motors and switches to work and perform useful mechanical action at the macroscopic level. Here, we review these recent developments. We show how modern research has embraced the full complexity of the molecular world by aiming at the design of autonomous, and sometimes adaptive, molecular systems that work continuously under the effect of illumination. We report evidence that molecular motion can be engineered into highly sophisticated movements and that, from a fundamental point of view, continuous movement can only emerge when man-made molecules cooperate, in space and time. Eventually, unravelling the rules of molecular motion will support the creation of molecular materials that produce work continuously under a constant input of energy.The natural world has long provided inspiration for the production of artificial, adaptive materials. This Review discusses how unravelling the rules of molecular motion has enabled integration of the cooperative, and sometimes synchronized, operation of light-responsive molecular machines, across length scales, into responsive and autonomous matter.
The motion of artificial molecular machines has been amplified into the shape transformation of polymer materials that have been compared to muscles, where mechanically active molecules work together ...to produce a contraction. In spite of this progress, harnessing cooperative molecular motion remains a challenge in this field. Here, we show how the light-induced action of artificial molecular switches modifies not only the shape but also, simultaneously, the stiffness of soft materials. The heterogeneous design of these materials features inclusions of free liquid crystal in a liquid crystal polymer network. When the magnitude of the intrinsic interfacial tension is modified by the action of the switches, photo-stiffening is observed, in analogy with the mechanical response of activated muscle fibers, and in contrast to melting mechanisms reported so far. Mechanoadaptive materials that are capable of active tuning of rigidity will likely contribute to a bottom-up approach towards human-friendly and soft robotics.
Self-reproducing molecules abound in nature where they support growth and motion of living systems. In artificial settings, chemical reactions can also show complex kinetics of reproduction, however ...integrating self-reproducing molecules into larger chemical systems remains a challenge towards achieving higher order functionality. Here, we show that self-reproducing lipids can initiate, sustain and accelerate the movement of octanol droplets in water. Reciprocally, the chemotactic movement of the octanol droplets increases the rate of lipid reproduction substantially. Reciprocal coupling between bond-forming chemistry and droplet motility is thus established as an effect of the interplay between molecular-scale events (the self-reproduction of lipid molecules) and microscopic events (the chemotactic movement of the droplets). This coupling between molecular chemistry and microscopic motility offers alternative means of performing work and catalysis in micro-heterogeneous environments.
The physico-chemical processes supporting life's purposeful movement remain essentially unknown. Self-propelling chiral droplets offer a minimalistic model of swimming cells and, in surfactant-rich ...water, droplets of chiral nematic liquid crystals follow the threads of a screw. We demonstrate that the geometry of their trajectory is determined by both the number of turns in, and the handedness of, their spiral organization. Using molecular motors as photo-invertible chiral dopants allows converting between right-handed and left-handed trajectories dynamically, and droplets subjected to such an inversion reorient in a direction that is also encoded by the number of spiral turns. This motile behavior stems from dynamic transmission of chirality, from the artificial molecular motors to the liquid crystal in confinement and eventually to the helical trajectory, in analogy with the chirality-operated motion and reorientation of swimming cells and unicellular organisms.
Transferring structural information from the nanoscale to the macroscale is a promising strategy for developing adaptive and dynamic materials. Here we demonstrate that the knotting and unknotting of ...a molecular strand can be used to control, and even invert, the handedness of a helical organization within a liquid crystal. An oligodentate tris(2,6-pyridinedicarboxamide) strand with six point-chiral centres folds into an overhand knot of single handedness upon coordination to lanthanide ions, both in isotropic solutions and in liquid crystals. In achiral liquid crystals, dopant knotted and unknotted strands induce supramolecular helical organizations of opposite handedness, with dynamic switching achievable through in situ knotting and unknotting events. Tying the molecular knot transmits information regarding asymmetry across length scales, from Euclidean point chirality (constitutional chirality) via molecular entanglement (conformation) to liquid-crystal (centimetre-scale) chirality. The magnitude of the effect induced by the tying of the molecular knots is similar to that famously used to rotate a glass rod on the surface of a liquid crystal by synthetic molecular motors.
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FZAB, GEOZS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Topology is a universal concept that is encountered in daily life and is known to determine many static and dynamical properties of matter. Taming and controlling the topology of materials therefore ...constitutes a contemporary interdisciplinary challenge. Building on the controllable spatial properties of soft matter appears as a relevant strategy to address the challenge, in particular, because it may lead to paradigmatic model systems that allow checking theories experimentally. Here we report experimentally on a wealth of complex free-standing metastable topological architectures at the micron scale, in frustrated chiral nematic droplets. These results support recent works predicting the formation of free-standing knotted and linked disclination structures in confined chiral nematic fluids. We also demonstrate that various kinds of external fields (thermal, electrical and optical) can be used to achieve topological remote control. All this may foster the development of new devices based on topologically structured soft media.
Liquid crystal polymer networks respond with an anisotropic deformation to a range of external stimuli. When doped with molecular photoswitches, these materials undergo complex shape modifications ...under illumination. As the deformations are reversed when irradiation stops, applications where the activated shape is required to have thermal stability have been precluded. Previous attempts to incorporate molecular switches into thermally stable photoisomers were unsuccessful at photogenerating macroscopic shapes that are retained over time. Herein, we show that to preserve photoactivated molecular deformation on the macroscopic scale, it is important not only to engineer the thermal stability of the photoswitch but also to adjust the cross‐linking density in the polymer network and to optimize the molecular orientations in the material. Our strategy resulted in materials containing fluorinated azobenzenes that retain their photochemical shape for more than eight days, which constitutes the first demonstration of long‐lived photomechanical deformation in liquid‐crystal polymer networks.
Liquid crystal polymers that contain fluorinated azobenzenes and retain a photochemically generated shape for more than eight days are reported. To preserve photoactivated molecular deformation on the macroscopic scale, the thermal stability of the photoswitch, the cross‐linking density in the polymer network, and the molecular orientations in the material have been optimized.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Azobenzene is a widely used guest molecule to build up dynamic photo-responsive host-guest systems. Here, we studied the host-guest complexation of a water-soluble, ortho-fluorinated azobenzene with ...two different host molecules, a cyclodextrin (β-CD) and a cucurbit8uril (CB8), and demonstrate that in the presence of both, the guest forms two stable supramolecular complexes selectively. In its trans-form, it favors binding to β-CD, whereas in its cis-form it favors complexation to CB8. Upon light-triggered photo-isomerization, the photoswitch was reversibly and selectively transferred from one host cavity to the other. This light-driven host exchange provides a new tool for supramolecular systems.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
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