Single-Molecule Fluorescence Spectroscopy of Perylene Diimide Dyes in a γ‑Cyclodextrin Film: Manifestation of Photoinduced H‑Atom Transfer via Higher Triplet (n, π) Excited States

Supramolecular complexation of γ-cyclodextrin (γ-CD) with N,N′-bis­(2,6-dimethylphenyl)­perylene-3,4,9,10-tetracarboxylic diimide (DMP-PDI) or N,N′-bis­(2,6-dioctyl)­perylene-3,4,9,10-tetracarboxylic diimide (C8-PDI) dye in an aqueous solution and in a γ-CD solid film were investigated via ensemble and single-molecule fluorescence spectroscopy. These two perylene diimide derivatives possess almost the same electronic structure but have different terminal functional groups. This structural difference leads to formation of an inclusion complex of γ-CD with DMP-PDI but not with C8-PDI in aqueous solution. In a γ-CD solid film, the distributions of the wavelengths of emission maximum (λmax em) are strikingly different between these two dyes; a much narrower and blue-shifted λmax em distribution was observed for C8-PDI relative to DMP-PDI. This difference is attributed to the fact that the C8-PDI molecules are bound at the γ-CD/glass interface as a result of spin-coating of the sample solution, whereas the DMP-PDI molecules form 1:1 and 1:2 inclusion complexes with conformational heterogeneities in the film. In comparison to the case for C8-PDI, more frequent on–off blinking events were observed for DMP-PDI. The blinking statistics of DMP-PDI in the γ-CD film exhibit both single-exponential and nonexponential (i.e., dispersive) kinetics, revealed by robust statistical analysis. Energetic consideration with the aid of theoretical calculations suggests that the underlying photophysics most probably involves hydrogen atom transfer (HAT) between the DMP-PDI guest and γ-CD host via higher excited (n, π*) triplet states. The hypothesis of HAT in the inclusion complex reasonably explains the experimental results; however, a charge transfer hypothesis cannot explain the results. The dispersive kinetics is attributable to the effect of thermal fluctuation in the forward and backward HAT reactions.