Amphiphilic molecules, comprising hydrophobic and hydrophilic moieties and the intrinsic propensity to self‐assemble in aqueous environment, sustain a fascinating spectrum of structures and functions ranging from biological membranes to ordinary soap. Facing the challenge to design responsive, adaptive, and out‐of‐equilibrium systems in water, the incorporation of photoresponsive motifs in amphiphilic molecular structures offers ample opportunity to design supramolecular systems that enables functional responses in water in a non‐invasive way using light. Here, we discuss the design of photoresponsive molecular amphiphiles, their self‐assembled structures in aqueous media and at air–water interfaces, and various approaches to arrive at adaptive and dynamic functions in isotropic and anisotropic systems, including motion at the air–water interface, foam formation, reversible nanoscale assembly, and artificial muscle function. Controlling the delicate interplay of structural design, self‐assembling conditions and external stimuli, these responsive amphiphiles open several avenues towards application such as soft adaptive materials, controlled delivery or soft actuators, bridging a gap between artificial and natural dynamic systems.

Harvesting energy and converting it into mechanical motion forms the basis for both natural and artificial molecular motors. Overcrowded alkene-based light-driven rotary motors are powered through sequential photochemical and thermal...

Molecular photoactuators can control shape and chemical or physical properties of the responsive system they are embedded in. These effects are usually mediated by supramolecular interactions and can be amplified to perform work at the microand macroscopic scale, for instance, in materials and biomimetic systems. While many studies focus on the observable outcome of these events, photoresponsive structures can also translate their conformational change to molecular components and perform work against random Brownian motion. Stereochemical cascades can amplify light-generated motion to a distant moiety of the same molecule or molecular assembly, via conformationally restricted stereogenic elements. Being able to control the conformation or motion of molecular systems remotely provides prospects for the design of the smallest machines imaginable. This Focus Review emphasizes the emergence of directed, coupled motion of remote functionalities triggered by light-powered switches and motors as a tool to control molecular topology and function.

Diarylamines find use as metal ligands and as structural components of drug molecules, and are commonly made by metal-catalyzed C-N coupling. However, the limited tolerance to steric hindrance of these couplings restricts the synthetic availability of more substituted diarylamines. Here we report a remarkable variant of the Smiles rearrangement that employs readily accessible N-aryl anthranilamides as precursors to diarylamines. Conformational predisposition of the anthranilamide starting material brings the aryl rings into proximity and allows the rearrangement to take place despite the absence of electron-withdrawing substituents, and even with sterically encumbered doubly ortho-substituted substrates. Some of the diarylamine products are resolvable into atropisomeric enantiomers, and are the first simple diarylamines to display atropisomerism.

Controlling dynamic stereochemistry is an important challenge, as it is not only inherent to protein structure and function but often governs supramolecular systems and selfassembly. Typically, disulfide bonds exhibit stereodivergent behavior in proteins; however, how chiral information is transmitted to disulfide bonds remains unclear. Here, we report that hydrogen bonds are essential in the control of disulfide chirality and enable stereodivergent chirality transfer. The formation of S−S•••H−N hydrogen bonds in solution can drive conformational adaption to allow intramolecular chirality transfer, while the formation of C=O•••H−N hydrogen bonds results in supramolecular chirality transfer to form antiparallel helically selfassembled solid-state architectures. The dependence on the structural information encoded in the homochiral amino acid building blocks reveals the remarkable dynamic stereochemical space accessible through noncovalent chirality transmission.