| Summary: | We report theoretical investigations on azobenzene-based indandiazocines, novel chiral systems
that perform unidirectional cis↔trans isomerizations upon photo-excitation. For three different
systems of this kind, we have simulated excited-state surface-hopping trajectories for both
isomerization directions, using a configuration-interaction treatment based on system-specifically
reparametrized semiempirical AM1 theory. Our results are also compared to experimental and
theoretical results for the parent system diazocine. We show that, as intended by design, the
trans→cis bending of the azo unit in these indandiazocines can only happen in one of the two
possible directions due to sterical constraints, which is a new feature for photoswitches and a necessary prerequisite for directional action at the nanoscale.
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