Panchromatic Light-Capturing Bis-styryl BODIPY-Perylenediimide Donor-Acceptor Constructs: Occurrence of Sequential...

Two wide-band-capturing donor-acceptor conjugates featuring bis-styrylBODIPY and perylenediimide (PDI) have been newly synthesized, and the occurrence of ultrafast excitation transfer from the ¹ PDI* to BODIPY, and a subsequent electron transfer from the ¹ BODIPY* to PDI have been demonstrated. Optical absorption studies revealed panchromatic light capture but offered no evidence of ground-state interactions between the donor and acceptor entities. Steady-state fluorescence and excitation spectral recordings provided evidence of singlet-singlet energy transfer in these dyads, and quenched fluorescence of bis-styrylBODIPY emission in the dyads suggested additional photo-events. The facile oxidation of bis-styrylBODIPY and facile reduction of PDI, establishing their relative roles of electron donor and acceptor, were borne out by electrochemical studies. The electrostatic potential surfaces of the S₁ and S₂ states, derived from time-dependent DFT calculations, supported excited charge transfer in these dyads. Spectro-electrochemical studies on one-electron-oxidized and one-electron-reduced dyads and the monomeric precursor compounds were also performed in a thin-layer optical cell under corresponding applied potentials. From this study, both bis-styrylBODIPY⋅⁺ and PDI⋅^- could be spectrally characterizes and were subsequently used in characterizing the electron-transfer products. Finally, pump-probe spectral studies were performed in dichlorobenzene under selective PDI and bis-styrylBODIPY excitation to secure energy and electron-transfer evidence. The measured rate constants for energy transfer, k_ENT , were in the range of 10¹¹  s^-1 , while the electron transfer rate constants, k_ET , were in the range of 10¹⁰  s^-1 , thus highlighting their potential use in solar energy harvesting and optoelectronic applications.