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The last decade has witnessed rapid developments in aggregation‐induced emission (AIE). In contrast to traditional aggregation, which causes luminescence quenching (ACQ), AIE is a reverse phenomenon that allows robust luminescence to be retained in aggregated and solid states. This makes it possible to fabricate various highly efficient luminescent materials, which opens new paradigms in a number of fields, such as imaging, sensing, medical therapy, light harvesting, light‐emitting devices, and organic electronic devices. Of the various important features of AIE molecules, their self‐assembly behavior is very attractive because the formation of a well‐defined emissive nanostructure may lead to advanced applications in diverse fields. However, due to the nonplanar topology of AIEgens, it is not easy for them to self‐assemble into well‐defined structures. To date, some strategies have been proposed to achieve the self‐assembly of AIEgens. Herein, we summarize the most recent approaches for the self‐assembly of AIE molecules. These approaches can be sorted into two classes: 1) covalent molecular design and 2) noncovalent supramolecular interactions. We hope this will inspire more excellent work in the field of AIE. AIEgens assemble! The nonplanar topology of AIEgens makes it difficult for them to self‐assemble into well‐defined structures. However, by using appropriate covalent molecular design and noncovalent supramolecular interactions, the elegant self‐assembly of AIEgens can be achieved too. [ABSTRACT FROM AUTHOR]

Transient structures play a wide range of vital roles in biological systems. Different from static structures that form the skeleton of bio‐tissues, transient structures only occur at certain spatial and temporal scales to undertake their duties in the life circle. Despite the significant progress in the field of artificial molecular self‐assembly studies, it still remains challenging to construct functional transient structures. Herein, the shaping of transient coordinating self‐assembled structures and their fluorescence is reported via host‐guest interaction that disfavors the assembly. The host‐guest interaction between the luminescent ligand and cyclodextrin drastically changes the kinetics of the coordinating self‐assembly, enabling the formation of transient structures. Different from the static equilibrium one with typical monomer emission in the UV region, the transient self‐assembly forms excimers, leading to visible emission. More intriguingly, the life cycle of the transient structures can be easily modulated by varying the host‐guest ratio, ligand‐metal ratio, as well as temperature. This makes it possible to create living patterns that mimic the growth of plants at different life stages. It is therefore envisioned that the creation of transient molecular self‐assembly will open a new paradigm in the field of molecular self‐assembly featuring advanced materials with dynamic functions. [ABSTRACT FROM AUTHOR]

Repeated programmability has emerged as a desired property in smart device engineering, but the programmability will fatigue upon repeated applications due to the unmatched mechanical property between the layer materials and the polymeric glue that is required to integrate the two individual oriented layers. It is reported here that glue‐free antifatigue programmable laminate materials can be made with films resulted from solid‐phase molecular self‐assembly (SPMSA). The SPMSA films are created by squeezing the precipitates of oppositely charged polyelectrolytes and DTAB with a noodle machine, where the hydrophobic DTAB molecules self‐assembled into wormlike micelles and oriented along the squeezing direction. The surface molecules in this film are endowed with sufficient mobility in the presence of hydration water, so that two such films are able to be pressed into a laminate material owing to the hydrophobic and electrostatic interactions between the molecules on the two adjacent surfaces. As the water evaporated gradually, the left laminate materials are glue‐free with the same composition. When many of such films are integrated with specific designs, complicated shape programming is able to be achieved, and the programmability is reversible without fatigue. The current strategy is envisioned as a potent intriguing pathway leading to advanced programable materials. [ABSTRACT FROM AUTHOR]

The co‐assembly of spherical colloids and surfactant–cyclodextrin microtubes yields a library of dynamic colloid‐in‐tube structures, including helices. In situ observations of these structures, including their thermo‐reversible assembly and disassembly, demonstrate the potential of the interplay between molecular and colloidal self‐assembly, thereby providing a novel route to temperature‐sensitive particle alignment and release. [ABSTRACT FROM AUTHOR]

Anisotropic and binary colloids self-assemble into a variety of novel supracolloidal structures within the thermo-switchable confinement of molecular microtubes, achieving structuring at multiple length scales and dimensionalities. The multistage self-assembly strategy involving hard colloidal particles and a soft supramolecular template is generic for colloids with different geometries and materials as well as their binary mixtures. The colloidal architectures can be controlled by colloid shape, size, and concentration. Colloidal cubes align in chains with face-to-face arrangement, whereas rod-like colloids predominantly self-organize in end-to-end configurations with their long axis parallel with the long axis of the microtubes. The 1D microconfinement imposed on binary mixtures of anisotropic and isotropic colloids further increases the diversity of colloid-in-tube structures. In cube-sphere mixtures, cubes may act as additional confiners, locking in colloidal sphere chains, while a 'colloidal Morse code' is generated where rods and spheres alternate in the case of rod-sphere mixtures. The versatile confined colloidal superstructures including their thermoresponsive assembly and disassembly are relevant for the development of stimulus-responsive materials where controlled release and encapsulation are desired. [ABSTRACT FROM AUTHOR]

Hierarchical self‐assembly is often exploited by nature to build complex functional entities. A similar approach yielded a library of dynamic colloid‐in‐tube structures, such as colloidal zigzags, double‐ and triple‐helices, by utilizing the thermo‐reversible co‐assembly of colloidal spheres and molecular microtubes, as reported by J. Huang, A. V. Petukhov, et al. in their Communication on page 3364 ff. The assembly and disassembly of these structures near human body temperature was explored in situ and in real time. [ABSTRACT FROM AUTHOR]

Hierarchical, bottom‐up, self‐organization processes of nano‐ and microscale building blocks constitute an important design route for stimulus‐responsive materials. On page 313, Andrei V. Petukhov and co‐workers demonstrate that a rich variety of novel supracolloidal structures emerge from the self‐organization of various shape‐anisotropic colloids and binary mixtures of isotropic and anisotropic colloids in 1D microconfinement. [ABSTRACT FROM AUTHOR]