Intramolecular excimers of open forms of 2-benzopyran, 2- and 3-naphthopyrans in solution: TD-DFT/DFT analysis.

We hypothesized that in the open forms of diphenyl-substituted photochromic compounds, immediately after the photoinduced cleavage of the C-O bond, one of the phenyl rings forms a stack with an aromatic system at the other end of the alkyl linker. The formation of these intramolecular stacking excimers is made possible by a known increase in the rotational mobility of the linker double bonds in the excited state. The flexibilities of linkers are analyzed in terms of changes in their dihedral angles.