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Crystals of trans-3,3′-dimethylazobenzene (DMAB) exhibit crawling motion on solid surface upon simultaneous exposure to ultraviolet (UV) and visible light from opposite directions. In this study, the shape and velocity during the photoinduced crawling motion of DMAB crystals are successfully controlled by irradiation light intensities. A higher intensity of the visible light than the UV light causes the crystals to be spread shape and move slower (∼1 μm min−1). In contrast, a stronger UV light allows them to be droplet-like shape and move faster (∼4 μm min−1). The shape and velocity can be varied by adjusting the light intensities. Shape transformation is effectively applied to cargo capture–carry–release tasks. In particular, spread-shaped crystals capture silica particles over a wide area, whereas droplet-like crystals gather and transport them. This result suggests that a multifunctional soft transporter composed of a single component does not require complex fabrication, thereby contributing to the fields of soft robotics and microfluidics. [ABSTRACT FROM AUTHOR]

Here we present a study on the solid state properties of trans tetra-ortho-bromo azobenzene (4Br-Azo). Two distinct crystal polymorphs were identified: the α-phase and β-phase. Notably, only the β-phase exhibited an extraordinary photosalient effect (jumping/breaking) upon exposure to a wide range of visible light. Powder X-ray diffraction and Raman spectroscopy revealed that the β-phase is metastable and can transition to the α-phase when subjected to specific stimuli like heat and light. Furthermore, single crystal X-ray diffraction and density functional theory calculations highlighted the significance of a highly strained conformer in the β-phase, showing that the metastability of the phase potentially arises from relieving this strain. This metastability leads to a light induced phase transition, which appears to be the cause of the photosalient effect in these crystals. Interestingly the polymorphism at the core of 4Br-Azo's dynamic behavior is based on different arrangements of halogen based intermolecular interactions. It is possible that continued study on combining visible light capturing chromophores with halogen interaction-based polymorphism will lead to the discovery of even more visible light controlled dynamic crystal materials. [ABSTRACT FROM AUTHOR]

Emission‐switchable fluorophores often include stimuli‐responsive units in their molecular structures. This strategy works well, but the applicable compounds are limited to the derivatives of several kinds of photochromic molecules such as diarylethene, azobenzene, and spiropyran. Here, this work presents a simple methodology based on a photoresponsive precipitant for achieving color‐switchable photoluminescence. A luminescent dye, cyano‐substituted oligo(phenylenevinylene) (COPV), features both twisted intramolecular charge transfer and aggregation‐induced emission shift properties, leading to the change in the luminescence color from green to red upon precipitation. The COPV, together with photoisomerizable precipitant azobenzene (C6), is doped into spherical droplets of epoxy resin (ER) in a liquid state. The photoisomerization of C6 induced by UV irradiation and heating alternatively precipitates out and dissolves COPV in ER and changes the photoluminescence color, while maintaining the optical microresonator properties. This study will open a promising way for assembling/disassembling novel emission color‐switchable systems. [ABSTRACT FROM AUTHOR]

The spatial organization of polycyclic aromatic molecules during adhesion on a solid/liquid interface is the key event of a plethora of natural and industrial processes. Herein, we report the supramolecular assembly of violanthrone‐79—a model of asphaltenes, an intractable mixture of polycyclic aromatics from crude oil—at the solid‐liquid interface between highly oriented pyrolytic graphite (HOPG) and a hydrophobic medium (1‐phenyloctane). High‐resolution scanning tunneling microscopy revealed that molecules of violanthrone‐79 readily self‐assemble on the surface in supramolecular "nanoring" structures. The lattice parameters of the 2D unit cell are on the same order as those determined from a bulk single crystal. Transmission electron microscopy showed long‐range ordered patterns, and the spacing between the fringes is in agreement with the inter‐planar distances between aromatic cores of molecules that are helically arranged around the [001] axis in the 3D crystal. The results confirm that upon adsorption on solid/liquid interfaces, polycyclic aromatic molecules such as violanthrone‐79 form supramolecular assemblies by interaction with the substrate and self‐association, and this process could be the initial step of deposition of asphaltenes on carbonaceous oil reservoir walls and production tubing. [ABSTRACT FROM AUTHOR]