Molecular machines are at the frontier of biology and chemistry. The ability to control molecular motion and emulating the movement of biological systems are major steps towards the development of responsive and adaptive materials. Amazing progress has been seen for the design of molecular machines including light‐induced unidirectional rotation of overcrowded alkenes. However, the feasibility of inducing unidirectional rotation about a single bond as a result of chemical conversion has been a challenging task. In this Review, an overview of approaches towards the design, synthesis, and dynamic properties of different classes of atropisomers which can undergo controlled switching or rotation under the influence of a chemical stimulus is presented. They are categorized as molecular switches, rotors, motors, and autonomous motors according to their type of response. Furthermore, we provide a future perspective and challenges focusing on building sophisticated molecular machines.

Imines are photoaddressable motifs useful in the development of new generations of molecular switches, but their operation with low‐energy photons and control over isomer stability remain challenging. Based on a computational design, we developed phenylimino indolinone (PIO), a green‐light‐addressable T‐type photoswitch showing negative photochromism. The isomerization behavior of this photoactuator of the iminothioindoxyl (ITI) class was studied using time‐resolved spectroscopies on time scales from femtoseconds to the steady state and by quantum‐chemical analyses. The understanding of the isomerization properties and substituent effects governing these photoswitches opens new avenues for the development of novel T‐type visible‐light‐addressable photoactuators based on C=N bonds.

Circular polarized light is utilized in communication and display technologies and a major challenge is to develop systems that can be switched between left and right circular polarized luminescence with high degrees of polarization and enable multiple addressable stable states. Luminescent dyes in Liquid Crystal (LC) cholesteric phases are attractive systems to generate, amplify and modulate circularly polarized luminescence (CPL). In the present study, we employ light‐driven molecular motors as photo‐controlled chiral dopants in LCs to switch the handedness of the LC and the circular polarization of luminescence from an achiral dye embedded in the mesogenic material. Tuning of the color of the CPL and the retention time of the photoprogrammed helicity is demonstrated making use of a variety of motors and dyes. The flexibility offered by the design based on inherently chiral unidirectional rotary motors provides full control over CPL non‐invasively by light, opening possibilities for pixilated displays with externally addressable polarization.

Photoactuators and photoluminescent dyes utilize light to perform mechanical motion and undergo spontaneous radiation emission, respectively. Combining these two functionalities in a single molecule would benefit the construction of advanced molecular machines. Due to the possible detrimental interaction between the two light-dependent functional parts, the design of hybrid systems featuring both functions in parallel remains highly challenging. Here, we develop a light-driven rotary molecular motor with an efficient photoluminescent dye chemically attached to the motor, not compromising its motor function. This molecular system shows efficient rotary motion and bright photoluminescence, and these functions can be addressed by a proper choice of excitation wavelengths and solvents. The moderate interaction between the two parts generates synergistic effects, which are beneficial for lower-energy excitation and chirality transfer from the motor to the photoluminescent dye. Our results provide prospects towards photoactive multifunctional systems capable of carrying out molecular rotary motion and tracking its location in a complex environment.

Light‐induced 9,10‐phenanthrenequinone‐electron‐rich alkene (PQ‐ERA) photocycloadditions are an attractive new type of photoclick reaction, featuring fast conversions and high biocompatibility. However, the tunability of the reaction was hardly investigated up to now. To this end, we explored the influence of substituents on both reaction partners and the reaction rate between the PQs and ERAs. We identified new handles for functionalization and discovered that using enamines as ERAs leads to drastically enhanced rates (>5400 times faster), high photoreaction quantum yields (Φ_P, up to 65 %), and multicolor emission output as well as a high fluorescence quantum yield of the adducts (Φ_F, up to 97 %). Further investigation of the photophysical and photochemical properties provided insights to design orthogonal reaction systems both in solution and on nanoparticle surfaces for ultrafast chemoselective functionalization by photoclick reactions.