Moreover, their different spatial distribution indicates (partial) charge transfer character for the transition to the lowest excited singlet, which might explain the dependence of the photocyclization yield of 28 with the solvent polarity. On the other hand, simulations of the structural relaxation on the S1 potential energy surface of 28 in polar environments (Figure ) do not favor the orthogonal disposition of thiophene side groups with respect to the maleic anhydride backbone, which questions the role of the twisted intramolecular charge transfer state. Compounds 30-38 are discussed in the SI (Figures and).