Twisted intramolecular charge transfer (TICT) formation in hemithioindigo photoswitches has recently been reported and constitutes a second deexcitation pathway complementary to photoisomerization. Typically, this behavior is not found for this type of photoswitches, and it takes special geometric and electronic conditions to realize it. Here we present a systematic study that identifies the molecular preconditions leading to TICT formation in donor substituted hemithioindigo, which can thus serve as a frame of reference for other photoswitching systems. By varying the substitution pattern and providing an in-depth physical characterization including time-resolved and quantum yield measurements, we found that neither ground-state pretwisting along the rotatable single bond nor the introduction of strong push-pull character across the photoisomerizable double bond alone leads to formation of TICT states. Only the combination of both ingredients produces light-induced TICT behavior in polar solvents.
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