Probing conformational dynamics in single donor-acceptor synthetic molecules by means of photoinduced reversible electron transfer

Cotlet et al. 10.1073/pnas.0406119101.

Supporting Information

Files in this Data Supplement:

Supporting Text
Supporting Figure 6
Supporting Figure 7
Supporting Figure 8
Supporting Figure 9

Supporting Figure 6

Fig. 6. Energetically optimized structures of PN16 (A) and PN8 (B). (C) D-A distance distributions for PN16 (black) and PN8 (gray) calculated from the structures shown in A and B. Distance was estimated, for each triphenylamine donor, from the nitrogen to the edge of the perylenediimide.

Supporting Figure 7

Fig. 7. (A) Normalized absorption and fluorescence spectra of PN16 (dash, dash + circle) and PN8 (line, line + circle) in toluene. (B and C) Fluorescence decays and fits of PN16 in methylcyclohexane (raw, black; fit, gray), toluene (raw, green; fit, black) (B) and of PN16 in methylcyclohexane (raw, black; fit, gray), toluene (raw, green; fit, black), and ethyl acetate (raw, red; fit, black) (C).

Supporting Figure 8

Fig. 8. (A) Energetic scheme accounting for reversible ET in single PN16 and PN8 molecules immobilized in PS. t ₀, fluorescence lifetime of unquenched perylenediimide; k_forw and k_back, forward and reverse ET rate constants; k_CSS-GS, rate constant accounting for the deactivation of the CSS to the GS. (B) Correlation between the reverse ET rate constant and reverse ET decay time of the single PN16 molecule accounting for the data from Fig. 4A.

Fig. 9. (A) Rate constant for ET vs. D-A distance computed for through-space (line, b= 1.4 Å^-1) and through-bond (dashed line, b= 0.7 Å^-1) ET. Vertical dashed lines indicate the smallest D-A distances in PN8 and PN16 as predicted by molecular modeling calculations. (B) Square of the electronic coefficient vs. torsional angle correlation calculated from the structure shown in Inset by rotating, from 40° to 90°, the dihedral angle between the adjacent phenyl rings next to the triphenylamines. (C and D) Electronic coefficient (Q²) calculated for meta- (C) and para- (D) substitutedtriphenylamine-polyphenylene-perylenediimide branches. Arrows indicate the position of the carbon atom where Q² was estimated.