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folding and unfolding phenomenon, in which varying degrees of
electronic coupling between adjacent chromophores occurs.
Figure 5.23
Monomer, trimer, and hexamer structures are shown as
folded
-stacks and the trimer is used to manifest their
photoinduced dynamics. Spectra (a) through (e) are the
common single-molecule spectral shapes observed for
monomer (a
π
−
−
−
e). Portions
of spectral trajectories for a single trimer (f) and hexamer
(g) displaying dynamic emission color switches, indicating
folding, unfolding, and refolding. Twenty frames at 2 s
integration/spectrum =
b), trimer (a
e), and hexamer (a
∼
40 s total elapsed time.
π−π
The range of spectra observed is an indicator of the range of
interaction between adjacent chromophores. Emission following
normal Franck
−
Condon progression (535, 575, and 625 nm, Fig.
5.23a) is attributed to the localized emission from individual free
perylene molecules, while vibronically resolved yellow (Fig. 5.23c)
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