Photodriven molecular motors are able to convert light energy into directional motion and hold great promise as miniaturized powering units for future nanomachines. In the current state of the art, considerable efforts have still to be made to increase the efficiency of energy transduction and devise systems that allow operation in ambient and non-damaging conditions with high rates of directional motions. The need for ultraviolet light to induce the motion of virtually all available light-driven motors especially hampers the broad applicability of these systems. We describe here a hemithioindigo-based molecular motor, which is powered exclusively by nondestructive visible light (up to 500 nm) and rotates completely directionally with kHz frequency at 20 °C. This is the fastest directional motion of a synthetic system driven by visible light to date permitting materials and biocompatible irradiation conditions to establish similarly high speeds as natural molecular motors.

Hemithioindigo-based molecular motors are powered by nondamaging visible light and provide very fast directional rotations at ambient conditions. Their ground state energy profile has been probed in detail, but the crucial excited state processes are completely unknown so far. In addition, very fast processes in the ground state are also still elusive to date and thus knowledge of the whole operational mechanism remains to a large extent in the dark. In this work we elucidate the complete lightdriven rotation mechanism by a combination of multiscale broadband transient absorption measurements covering a time scale from fs to ms in conjunction with a high level theoretical description of the excited state. In addition to a full description of the excited state dynamics in the various time regimes, we also provide the first experimental evidence for the elusive fourth intermediate ground state of the original HTI motor. The fate of this intermediate also is followed directly proving complete unidirectionality for both 180°rotation steps. At the same time, we uncover the hitherto unknown involvement of an unproductive triplet state pathway, which slightly diminishes the quantum yield of the E to Z photoisomerization. A rate model analysis shows that increasing the speed of motor rotation is most effectively done by increasing the photoisomerization quantum yields instead of barrier reduction for the thermal ratcheting steps. Our findings are of crucial importance for improved future designs of any light-driven molecular motor in general to yield better efficiencies and applicability.

The first example of a bis-hemithioindigo (bis-HTI)-based molecular receptor was realized. Its folding and selective binding affinity for aromatic guest molecules can be precisely controlled by visible light and heat. The thermodynamically stable state of the bis-HTI is the s-shaped planar Z,Z-configuration. After irradiation with 420 nm light only the E,Z-configuration is formed in a highly selective photoisomerization. The E,Z-isomer adopts a helical conformation because of the implementation of repulsive steric interactions. The E,Z-configured helix is able to recognize electron-poor aromatic guests exclusively through polar aromatic interactions and also distinguishes between regioisomers. After heating, the Z,Z-configuration is completely restored and the aromatic guest molecule is efficiently released.

Efficiency and performance of light triggered molecular motors are crucial features that need to be mechanistically understood to improve the performance and enable conscious property tailoringf or specific applications. In this work, three differenth emithioindigo-based molecular motors are investigated and all four steps in their complete unidirectionalr otation are unraveled fully quantitatively. Transient absorption spectroscopy across twelveo rders of magnitude in time is used to probe the fs nuclear motions up to the ms thermal kinetics, covering the timeframe of the whole motor rotation. The newly knownf ull mechanisms allow simulation of the motor systems to scrutinize their performance at realistic illumination conditions. This highlights the importance of photoisomerization quantum yields for the rotationspeed. The substitution pattern in close proximity to the rotation axle influences the excited and ground state properties. Reduction of electron donation and concomitant increaseo fs teric hindrance leads to faster photoisomerization reactions with quasi-ballistic behavior,b ut also to as light decrease in the quantume fficiency. The expected decelerating effects of increased stericsa re primarily manifested in the ground state. Ap romising approach for nextgeneration hemithioindigom otors is to elevate electron donation at the rotor fragment followed by an increaseo f steric hindrance.

A series of bis-hemithioindigo photoswitches with different molecular setups are presented allowing precise manipulation of molecular shapes with visible light.