Global Performance Indices for Dynamic Crystals as Organic Thermal Actuators

Crystal adaptronics is an emergent materials science discipline at the intersection of solid-state chemistry and mechanical engineering that explores the dynamic nature of mechanically reconfigurable, motile, and explosive crystals. Adaptive molecular crystals bring to materials science a qualitatively new set of properties that associate long-range structural order with softness and mechanical compliance. However, the full potential of this class of materials remains underexplored and they have not been considered as materials of choice in an engineer's toolbox. A set of general performance metrics that can be used for quantification of the performance of these prospective dynamic materials as micro- and macroactuators is presented. The indices are calculated on two selected representatives of thermosalient solids—materials that undergo rapid martensitic transitions accompanied with macroscopic locomotion. Benchmarking of their performance against extensive set of data for the existing actuator classes and visualization using materials property charts uncover the hidden potential and advantages of dynamic crystals, while they also reveal their drawbacks for actual application as actuators. Altogether the results indicate that, if the challenges with fabrication and implementation in devices are overcome, adaptive molecular crystals can have far-reaching implications for emerging fields such as smart microelectronics and soft microrobotics.     

Introducing Defects in 3D Photonic Crystals: State of the Art

3D photonic crystals (PhCs) and photonic bandgap (PBG) materials have attracted considerable scientific and technological interest. In order to provide functionality to PhCs, the introduction of controlled defects is necessary; the importance of defects in PhCs is comparable to that of dopants in semiconductors. Over the past few years, significant advances have been achieved through a diverse set of fabrication techniques. While for some routes to 3D PhCs, such as conventional lithography, the incorporation of defects is relatively straightforward; other methods, for example, self‐assembly of colloidal crystals (CCs) or holography, require new external methods for defect incorporation. In this review, we will cover the state of the art in the design and fabrication of defects within 3D PhCs. The figure displays a fluorescence laser scanning confocal microscopy image of a y‐splitter defect formed through two‐photon polymerization within a CC.     

Helix Inversion Controlled by Molecular Motors in Multistate Liquid Crystals

Unravelling the rules of molecular motion is a contemporary challenge that promises to support the development of responsive materials and is likely to enhance the understanding of functional motion. Advances in integrating light-driven molecular motors in soft matter have led to the design and realization of chiral nematic (cholesteric) liquid crystals that can respond to light with modification of their helical pitch, and also with helix inversion. Under illumination, these chiral liquid crystals convert from one helical geometry to another. Here, a series of light-driven molecular motors that feature a rich configurational landscape is presented, specifically which involves three stable chiral states. The succession of chiral structures involved in the motor cycle is transmitted at higher structural levels, as the cholesteric liquid crystals that are formed can interconvert between helices of opposite handedness, reversibly. In these materials, the dynamic features of the motors are thus expressed at the near-macroscopic, functional level, into addressable colors that can be used in advanced materials for tunable optics and photonics.     

Exploration and Exploitation of Water in Colloidal Crystals

Water on solid surfaces is ubiquitously found in nature, in most cases due to mere adsorption from ambient moisture. Because porous structures have large surfaces, water may significantly affect their characteristics. This is particularly obvious in systems formed by separate particles, whose interactions are strongly influenced by small amounts of liquid. Water/solid phenomena, like adsorption, condensation, capillary forces, or interparticle cohesion, have typically been studied at relatively large scales down to the microscale, like in wet granular media. However, much less is known about how water is confined and acts at the nanoscale, for example, in the interstices of divided systems, something of utmost importance in many areas of materials science nowadays. With novel approaches, in‐depth investigations as to where and how water is placed in the nanometer‐sized pores of self‐assembled colloidal crystals have been made, which are employed as a well‐defined, versatile model system with useful optical properties. In this Progress Report, knowledge gained in the last few years about water distribution in such nanoconfinements is gathered, along with how it can be controlled and the consequences it brings about to extract new or enhance existing material functionalities. New methods developed and new capabilities of standard techniques are described, and the water interplay with the optical, chemical, and mechanical properties of the ensemble are discussed. Some lines for applicability are also highlighted and aspects to be addressed in the near future are critically summarized.     

Photonic Crystals from Emulsion Templates

Macroporous titania, which undergoes transition to the rutile phase by calcination without collapse of the pore structure, is obtained by polymerizing a titania sol suspended around “colloidal crystals” of oil droplets. The deformable template counteracts cracking of the titania phase. The Figure shows a scanning electron micrograph of a rutile sample with 200 nm pores obtained by the method described.     

Light-Responsive Colloidal Crystals Engineered with DNA

A novel method for synthesizing and photopatterning colloidal crystals via light-responsive DNA is developed. These crystals are composed of 10–30 nm gold nanoparticles interconnected with azobenzene-modified DNA strands. The photoisomerization of the azobenzene molecules leads to reversible assembly and disassembly of the base-centered cubic (bcc) and face-centered cubic (fcc) crystalline nanoparticle lattices. In addition, UV light is used as a trigger to selectively remove nanoparticles on centimeter-scale thin films of colloidal crystals, allowing them to be photopatterned into preconceived shapes. The design of the azobenzene-modified linking DNA is critical and involves complementary strands, with azobenzene moieties deliberately staggered between the bases that define the complementary code. This results in a tunable wavelength-dependent melting temperature (T_m) window (4.5–15 °C) and one suitable for affecting the desired transformations. In addition to the isomeric state of the azobenzene groups, the size of the particles can be used to modulate the T_m window over which these structures are light-responsive.