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.

Hemithioindigo molecular motors undergo very fast unidirectional rotation upon irradiation with visible light, which has prevented a complete analysis of their working mechanism. In this work, we have considerably slowed down their motion by using a new synthesis for sterically hindered motor derivatives. This method allowed the first observation of all four intermediate states populated during rotation. The exact order in which each isomeric state is formed under irradiation conditions was elucidated using low temperature H NMR spectroscopy in conjunction with other analytical methods. At the same time, complete unidirectionality could also be directly shown. Access to slowly rotating hemithioindigo motors opens up a plethora of new applications for visible-light-induced unidirectional motions, especially in areas such as catalysis, smart materials, and supramolecular chemistry.

We report on the synthesis of a hemithioindigo molecular motor bearing thioether feet for metal surface attachment and a comprehensive study of its light induced unidirectional motion in solution.

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

Hemithioindigo molecular motors undergo very fast unidirectional rotation upon irradiation with visible light, which has prevented ac omplete analysis of their working mechanism. In this work, we have considerably slowed down their motion by using an ew synthesis for sterically hindered motor derivatives.This method allowed the first observation of all four intermediate states populated during rotation. The exact order in whiche ach isomeric state is formed under irradiation conditions was elucidated using low temperature 1 HNMR spectroscopyi nc onjunction with other analytical methods.A tt he same time,c omplete unidirectionality could also be directly shown. Access to slowly rotating hemithioindigo motors opens up ap lethora of new applications for visible-light-induced unidirectional motions,especially in areas such as catalysis,smart materials,and supramolecular chemistry.