Supramolecular Chalcogen-Bonded Shape Memory Actuators.

Supramolecular liquid crystal elastomers (LCEs) incorporating chalcogen bonds (ChBs) have been synthesized and investigated for shape memory and actuation properties. LCEs featuring strong Se⋯N ChBs (−40 to −43 kJ mol−1) exhibit both shape memory effects (SME) and reversible actuation, while those with weaker S⋯N ChBs (−32 to −34 kJ mol−1) do not. The Se⋯N‐based LCEs transition from one‐way to two‐way SME after three days at room temperature, enabling programmable 2D/3D shape transformations and rewritable surface patterns. They also enable the fabrication of light‐powered crawling robots as well as temperature‐responsive knot‐like actuators. These results highlight the critical role of the ChB strength and specificity in designing functional materials. Solid‐state NMR, Raman spectroscopy, and density functional theory calculations provide further molecular‐level insights into ChB interactions, laying the groundwork for advanced supramolecular actuators and shape‐morphing LCEs.

This dissertation demonstrates the design of reversibly self-morphing novel liquid crystalline elastomer (LCE) antennas that can dynamically change electromagnetic performance in response to temperature. This change in performance can be achieved by programming the shape change of stimuli-responsive (i.e., temperature-responsive) LCEs, and using these materials as substrates for reconfigurable antennas. Existing reconfigurable antennas rely on external circuitry such as Micro-Electro-Mechanical-Systems (MEMS) switches, pin diodes, and shape memory alloys (SMAs) to reconfigure their performance. Antennas using MEMS or diodes exhibit low efficiency due to the losses from these components. Also, antennas based on SMAs can change their performance only once as SMAs response to the stimuli and is not reversible. Flexible electronics are capable of morphing from one shape to another using various techniques, such as liquid metals, hydrogels, and shape memory polymers. LCE antennas can reconfigure their electromagnetic performance, (e.g., frequency of operation, polarization, and radiation pattern) and enable passive (i.e., battery-less) temperature sensing and monitoring applications, such as passive radio frequency identification device (RFID) sensing tags. Limited previous work has been performed on shape-changing antenna structures based on LCEs. To date, self-morphing flexible electronics, including antennas, which rely on stimuli-responsive LCEs that reversibly change shape in response to temperature changes, have not been previously explored. Here, LCE antennas will be studied and developed. Also, the metallization of LCEs with different metal conductors and their fabrication process, by either electron beam (E-Beam) evaporation or optical gluing of the metal film will be observed. The LCE material can have a significant impact on sensing applications due to its reversible actuation that can enable a sensor to work repeatedly. This interdisciplinary research (material polymer science and electrical engineering) is expected to contribute to the development of morphing electronics, including sensors, passive antennas, arrays, and frequency selective surfaces (FSS).

Liquid crystal elastomers (LCEs) are shape-morphing materials whose large and reversible shape transformations are caused by the coupling between the mobile anisotropic properties of liquid crystal (LC) units and the rubber elastic of polymer networks. Their shape-changing behaviors under certain stimuli are largely directed by the LC orientation; therefore, various strategies have been developed to spatially modulate the LC alignments. However, most of these methods are limited as they require complex fabrication technologies or have intrinsic limitations in applicability. To address this issue, programmable complex shape changes in some LCE types, such as polysiloxane side-chain LCEs, thiol-acrylate main-chain LCEs, etc., were achieved by using a mechanical alignment programming process coupled with two-step crosslinking. Here, we report a polysiloxane main-chain LCE with programmable 2- and 3D shape-changing abilities that were created by mechanically programming the polydomain LCE with two crosslinking steps. The resulting LCEs exhibited a reversible thermal-induced shape transformation between the initial and programmed shapes due to the two-way memory between the first and second network structures. Our findings expand on the applications of LCE materials in actuators, soft robotics, and smart structures where arbitrary and easily programmed shape morphing is needed.

Liquid crystal elastomer (LCE) is a rubbery material composed of polymer chains and liquid crystals (LC). LCE is well known to undergo a shape transformation from the isotropic to the anisotropic phase. This shape transformation is caused by the nematic transition of the LC included in the LCE. However, the mechanism of this transformation is unknown because the interaction of LC with the bulk polymers is too complex. In this presentation, we extend the two-dimensional Finsler geometry model for membranes to a three-dimensional model for LCE. The Finsler geometry model for LCE is a coarse grained one: the Guassian bond potential S1 is obtained by extending the one for membranes, which is originally obtained by a simple extension of the Guassian bond potential for the linear chain polymer model. The continuous Hamiltonian, which contains S1 and the curvature energy S2, is discretized using a three-dimensional rigid sphere composed of tetrahedrons. We study the shape transformation as a phase transition between the isotropic and anisotropic phases and report the results of the transition order, obtained by the Monte Carlo simulations.

A method for fabricating long, soft, and reversibly actuatable liquid crystal elastomer (LCE) fibers by using direct ink write (DIW) printing was developed. Here, the LCE was produced based on a two-stage thermal-photo curingreaction between a difunctional acrylate monomer and thiol. The LCE ink, mixed with nanoclay to increase the viscosity, was extruded through a nozzle onto a rotating mandrel to obtain a long fiber. After printing, the fiber was first thermally cured on the mandrel, then mechanically stretched, and photocured to achieve liquid crystal chain alignment for stress-free reversible activation. Upon optimizing the ink viscosity and DIW printing parameters, long fibers (up to 1.5 m long from the laboratory) were obtained. The resulting fiber had a modulus of 2 MPa, 51% actuation strain, and a failure strain of well over 100%. The potential of these fibers for applications was demonstrated. The LCE fibers were knit, sewn, and woven to form a variety of smart textiles. The fiber was also used to mimic bicep muscles with both large activation force and activation strain. By incorporating further intelligent characteristics, such as conductivity and biosensing into a single fiber, the LCE fibers could be potentially used for smart clothing, soft robotics, and biomedical devices.

The monodomain nematic liquid crystal elastomer (LCE) is a nonporous material with one-dimension (1D) negative thermal expansion (NTE) along the direction of orientation. This stimuli-responsive size change is comparable with the contractile response of a muscle fibre. Recently, LCEs have become more and more popular and increasingly investigated as a full-fledged class of stimuli-responsive materials. However, the nematic LCE is limited to a single, unidirectional deformation unless complex hybrid architectures are made. We develop here a special LCE based on a liquid crystal polymer with an extraordinary phase transition sequence, “re-entrant nematic (NRe) – smectic A (SmA) – nematic (N) – isotropic (I) phase”, along with “prolate – oblate – weakly oblate – spherical” chain conformation evolution. In the aligned LCE film, these conformational changes of polymer chain are observed with the naked eye through their macroscopic translations into a unique sequence of “contraction – expansion – second expansion” deformations. Notably, a switch from NTE to positive thermal expansion (PTE) occurs upon heating. Moreover, a bilayer actuator composed of aligned and non-aligned LCE layers can perform 2D to 3D shape transformation with “curling – uncurling – second uncurling” actuation sequence. This LCE capable of multiple deformations in response to a single stimulus paves the way to multimodal single-material actuators. It provides a new strategy for the development of advanced materials with adjustable and multidirectional deformations.

Using (51)V magic angle spinning solid-state NMR spectroscopy and density functional theory calculations we have characterized the chemical shift and quadrupolar coupling parameters for two eight-coordinate vanadium complexes, [PPh(4)][V(v)(HIDPA)(2)] and [PPh(4)][V(v)(HIDA)(2)]; HIDPA = 2,2'-(hydroxyimino)dipropionate and HIDA = 2,2'-(hydroxyimino)diacetate. The coordination geometry under examination is the less common non-oxo eight coordinate distorted dodecahedral geometry that has not been previously investigated by solid-state NMR spectroscopy. Both complexes were isolated by oxidizing their reduced forms: [V(iv)(HIDPA)(2)](2-) and [V(iv)(HIDA)(2)](2-). V(iv)(HIDPA)(2)(2-) is also known as amavadin, a vanadium-containing natural product present in the Amanita muscaria mushroom and is responsible for vanadium accumulation in nature. The quadrupolar coupling constants, C(Q), are found to be moderate, 5.0-6.4 MHz while the chemical shift anisotropies are relatively small for vanadium complexes, -420 and -360 ppm. The isotropic chemical shifts in the solid state are -220 and -228 ppm for the two compounds, and near the chemical shifts observed in solution. Presumably this is a consequence of the combined effects of the increased coordination number and the absence of oxo groups. Density functional theory calculations of the electric field gradient parameters are in good agreement with the NMR results while the chemical shift parameters show some deviation from the experimental values. Future work on this unusual coordination geometry and a combined analysis by solid-state NMR and density functional theory should provide a better understanding of the correlations between experimental NMR parameters and the local structure of the vanadium centers.

The molecular dynamics of a series of organometallic complexes covalently bound to amorphous silica surfaces is determined experimentally using solid-state nuclear magnetic resonance (NMR) spectroscopy and density functional theory calculations (DFT). The determination is carried out for a series of alkylidene-based catalysts having the general formula [([triple bond]SiO)M(ER)(=CH(t)Bu)(R')] (M = Re, Ta, Mo or W; ER = C(t)Bu, NAr or CH2(t)Bu; R' = CH2(t)Bu, NPh2, NC4H4). Proton-carbon dipolar coupling constants and carbon chemical shift anisotropies (CSA) are determined experimentally by solid-state NMR. Room-temperature molecular dynamics is quantified through order parameters determined from the experimental data. For the chemical shift anisotropy data, we validate and use a method that integrates static values for the CSA obtained computationally by DFT, obviating the need for low-temperature measurements. Comparison of the room-temperature data with the calculations shows that the widths of the calculated static limit dipolar couplings and CSAs are always greater than the experimentally determined values, providing a clear indication of motional averaging on the NMR time scale. Moreover, the dynamics are found to be significantly different within the series of molecular complexes, with order parameters ranging from <S(z)> = 0.5 for [([triple bond]SiO)Ta(=CH(t)Bu)(CH2(t)Bu)2] and [([triple bond]SiO)Re([triple bond]C(t)Bu)(=CH(t)Bu)(CH2(t)Bu)] to <S(z)> = 0.9 for [([triple bond]SiO)Mo([triple bond]NAr)(=CH(t)Bu)(R') with R' = CH2(t)Bu, NPh2, NC4H4. The data also show that the motion is not isotropic and could be either a jump between two sites or more likely restricted librational motion. The dynamics are discussed in terms of the molecular structure of the surface organometallic complexes, and the orientation of the CSAs tensor at the alkylidene carbon is shown to be directly related to the magnitude of the alpha-alkylidene CH agostic interation.

Liquid crystal elastomers (LCEs) are a class of smart materials that combine the anisotropic properties of liquid crystals with the elasticity of polymers, enabling reversible metamorphosis (i.e., shape transformation) in response to external stimuli. This reversible metamorphosis makes them ideal for many applications including soft robotics, artificial muscles, sensors, actuators, responsive coatings, etc. Prior studies have designed LCE surfaces with superhydrophobicity (i.e., extreme repellency to high surface tension liquid like water), but the combination of reversible metamorphosis of LCEs with superomniphobicity (i.e., extreme repellency to both high and low surface tension liquids) is unexplored. In this work, we developed LCE-based superomniphobic surfaces with reversible metamorphosis by laser texturing followed by low surface energy surface modification. Our LCE-based superomniphobic surfaces display extreme repellence to both aqueous and organic liquids as well as reversible metamorphosis due to nematic-isotropic transition of LCE. Utilizing these properties, we demonstrated loss-less manipulation of aqueous and organic liquid droplets, enabling merging, mixing, chemical reaction and microfluidic gating. We envision that our LCE-based superomniphobic surfaces with reversible metamorphosis will pave the way towards a wide range of applications including microfluidic reactors, lab-on-chip technologies, adaptive liquid-handling devices, controlled drug delivery systems etc.

Liquid crystal elastomers (LCEs) with reversible thermal actuation are promising platforms for multifunctional flexible electronics. Herein, we present a PVDF/LM-LCE (PVDF, polyvinylidene fluoride; LM, liquid metal) composite in which PVDF is polymerized in situ within the LCE matrix to achieve seamless mechanical coupling and efficient stress transfer. LM nanodroplets enhance mechanical robustness, charge transport, and photothermal conversion, enabling LCEs to serve as photothermally driven transducers that amplify the piezoelectric and pyroelectric outputs in these flexible systems. The optimized composite achieves a pyroelectric coefficient of -4.81 nC·cm- 2·K- 1, 1.8 times higher than conventional PVDF films. Furthermore, the composite device powers two LEDs and digital sensors using low-grade photothermal fluctuations. This LCE-based light-driven thermomechanical-to-electrical conversion strategy offers a generalizable pathway for high-performance, flexible pyroelectric and piezoelectric energy-harvesting materials.

The advent of additive manufacturing (AM), commonly known as 3D printing, has enabled the rapid fabrication of complex structures previously unrealizable with traditional manufacturing techniques. Current approaches, however, are limited to single materials or single methodologies greatly limiting the potential scope of manufacturable products and components. Recently, our group has developed a novel multi-material multi-method (m4) 3D printer which integrates four AM technologies and two complementary technologies into one single platform. This allows for the fabrication of complex devices able to provide a wide range of functionalities ranging from stretchable electronics to self-sensing devices. To demonstrate these functionalities in the realm of printable electronics, multiple proof of concept printed circuit boards (PCBs) were fabricated which solve issues commonly encountered in 3D printed electronics such as high resolution or vertically integrated access (VIA) circuits. In addition, 3D printed smart structures able to respond to external stimulus, such as light or heat, have become highly desirable for applications ranging from soft robotics to implantable medical devices. Recently, our group has turned to liquid crystal elastomers (LCE), a class of active material able to generate large, rapid, and reversible actuations. Therefore, using the m4 3D printer, LCE-based smart structures requiring complex electronics were fabricated which can change their shape in response to an applied current. To demonstrate this, a smart, reconfigurable radio frequency (RF) antenna was 3D printed which can change its shape and operating frequency as a function of the applied current. These examples demonstrate the vast potential of m4 3D printing for creating smart, reconfigurable, and multi-functional structures.

Photoreactions of the alpha- and beta-polymorphs of trans-cinnamic acid were studied by (13)C CPMAS solid-state nuclear magnetic resonance spectroscopy, and the reactants and products were spectroscopically characterized in detail. Chemical shifts and chemical shift anisotropy tensors calculated using density functional theory (DFT) were found to be in good agreement with the experimental results and helped to identify the polymorphs and the individual assignments of reactant and photoproduct carbon atoms. The beta-polymorph is metastable. Its transformation into the alpha-cinnamic acid polymorph is monitored by temperature-dependent (13)C NMR spectroscopy. The transformation occurs at a very slow rate at room temperature but is highly accelerated at elevated temperatures. Analysis of the kinetics of the photoreaction shows that the beta-polymorph progresses at a slower rate compared to that of alpha-cinnamic acid. Based on chemical shift tensor values of reactants and products as obtained from 2D PASS spectra, the difference in reaction rates is suggested to be due to the higher amount of molecular reorientation of functional groups upon photoreaction and the larger distance between the reacting double bonds.

Many xeric plant leaves exhibit bending and twisting morphology, which may contribute to their important biological and physical functions adapted to drought and desert conditions. Revealing the relationships between various morphologies and functionalities can inspire device designs for meeting increasingly stringent environmental requirements. Here, demonstrated on the biomimetic bilayer ribbons made of liquid crystal elastomers, we reveal that the stimulus-induced morphological evolution of bending, spiraling, twisting and various coupling states among them can be selectively achieved and precisely tuned by designing the director orientations in liquid crystal elastomer bilayers. The mathematical models and analytical solutions are developed to quantify the morphology selection and phase transition of these liquid crystal elastomer ribbons for material design, as confirmed by experiments. Moreover, we show that, under activation and control of external stimuli, the twisting configuration can be harnessed to effectively collect and guide the transportation of droplets, and enhance the structural stiffness for resisting wind blow and rainfall to achieve the optimal configuration for water collection. Our results reveal the interesting functions correlated with bending, spiraling and twisting morphologies widely present in the natural world, by providing fundamental insights into their shape transformation and controlling factors. This work also demonstrates a potential application with integrating morphogenesis–environment interactions into devices or equipments.

Programming shape changes in soft materials requires precise control of the directionality and magnitude of their mechanical response. Among ordered soft materials, liquid crystal elastomers (LCEs) exhibit remarkable and programmable shape shifting when their molecular order changes. In this work, we synthesized, remotely programmed, and modeled reversible and complex morphing in monolithic LCE kirigami encoded with predesigned topological patterns in its microstructure. We obtained a rich variety of out-of-plane shape transformations, including auxetic structures and undulating morphologies, by combining different topological microstructures and kirigami geometries. The spatiotemporal shape-shifting behaviors are well recapitulated by elastodynamics simulations, revealing that the complex shape changes arise from integrating the custom-cut geometry with local director profiles defined by topological defects inscribed in the material. Different functionalities, such as a bioinspired fluttering butterfly, a flower bud, dual-rotation light mills, and dual-mode locomotion, are further realized. Our proposed LCE kirigami with topological patterns opens opportunities for the future development of multifunctional devices for soft robotics, flexible electronics, and biomedicine.

While liquid crystal elastomers (LCEs) are ideal materials for soft-robotic actuators, filling the role of muscle and shape-defining material simultaneously, it is non-trivial to give them ground state shapes beyond simple sheets or fibers. Here tubular LCE actuators scalable to arbitrary length are producedusing a continuous three-phase coaxial flow microfluidic process. By pumping an oligomeric precursor solution between inner and outer aqueous phases in a cylindrically symmetric nested capillary set-up, and by reducing the interfacial tension to negligible values using surfactants adapted to each phase, the tubular liquid flow is stabilized over distances more than 200 times the diameter or 2000 times the thickness. In situ photocrosslinking of the middle phase turns it into an LCE network that is flow-aligned by the shear gradient over the phase. The reversible actuation of the tubes upon heating yields a reduction of the interior space, pumping out enclosed fluid, and the relaxation upon cooling leads to the fluid being sucked back in. By moving a local heat source along the tube, it acts as a peristaltic pump. It is proposed that the tubes could, pending functionalization for light-triggered actuation, function as active synthetic vasculature in biologicalcontexts.