A systematic fluorescence and flash photolytic investigation of a series of covalently linked fullerene / ferrocene based donor-bridge-acceptor dyads is reported as a function of the nature of the bridge between the donor site and acceptor site. The fluorescence of the investigated dyads 2 (Φrel = 0.17 × 10−4, 3 (Φrel = 0.78 × 10−4), 4 (Φrel = 1.5 × 10−4), 5 (Φrel = 0.7 × 10−4), and 6 (Φrel = 2.9 × 10−4) were substantially quenched, relative to N-methyl fulleropyrrolidine (1) (Φrel = 6.0 × 10−4). Photolysis of N-methyl fulleropyrrolidine (1) in toluene revealed formation of the excited singlet state which was followed by a rapid intersystem crossing to the excited triplet state. On the other hand, the fate of the excited singlet state of 2, 3, 4, 5, and 6 was found to be governed by rapid intramolecular quenching, with rate constants of 28×109 s−1, 6.9×109 s−1, and 3.4×109 s−1, 14×109 s−1, 2.3×109 s−1 respectively. The electron transfer process and the charge separation were confirmed by monitoring the characteristic π-radical anion bands at λmax = 400 and 1055 nm in degassed benzonitrile with τ1/2 = 1.8 μs (3) and 2.5 μs (4).
Research on Chemical Intermediates – Springer Journals
Published: Apr 14, 2009
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