Affiliation:
1. Department of Chemistry University of North Texas at Denton 1155 Union Circle, #305070 Denton TX 76203-5017 USA
2. Área de Química Orgánica, Instituto de Bioingeniería Universidad Miguel Hernández Avda. de la Universidad s/n 03203 Elche Spain
3. Department of Physical Sciences and Mathematics Wayne State College 111 Main Street Wayne Nebraska 68787 USA
Abstract
AbstractTwo 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 1PDI* to BODIPY, and a subsequent electron transfer from the 1BODIPY* 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, kENT, were in the range of 1011 s−1, while the electron transfer rate constants, kET, were in the range of 1010 s−1, thus highlighting their potential use in solar energy harvesting and optoelectronic applications.
Funder
Directorate for Mathematical and Physical Sciences
Subject
General Chemistry,Catalysis,Organic Chemistry
Cited by
1 articles.
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