To resolve this apparent contradiction, we sampled the nearest-neighbor solvent arrangement a) at the moment of the electronic transition S1→S0 and b) after 200 fs relaxation dynamics in the S0-state (fig. ). For HTI solvation in hexane, such before/after analysis of nearby solvent atom distribution clearly shows the steric hindering effect: solvent atoms close to FP-PhC 7 are shoved aside during the hinge motion of the phenyl ring while the solvent on the opposing side of the stilbene moiety is following this motion. In stark contrast to this solvation mechanism, the coordinating DMSO molecule moves concertedly with the stilbene moiety to keep the hydrogenbonding pattern upright. Hence, the lower extend of steric hindrance experienced for HTI switching in DMSO may be related to a less dense solvation of the phenyl ring (fig. ) and the concerted rotation motion of DMSO coordinating the stilbene moiety (fig. ).