Probing the Effects of Electronic-Vibrational Resonance on the Rate of Excited-State Energy Transfer in Bacteriochlorin Dyads.

The impact of vibrational-electronic resonances on the rate of excited-state energy transfer is examined in a set of bacteriochlorin dyads that employ the same phenylethyne linker. The donor/acceptor excited-state energy gap is tuned from ∼200 to ∼1100 cm -1 using peripheral substituents on the donor and acceptor bacteriochlorin macrocycles. Ultrafast energy transfer is observed with rate constants of (0.3 ps) -1 to (1.7 ps) -1 , which agree with those predicted by Förster theory to within a factor of 2. Furthermore, the measured rates follow a trend-line with only small deviations that do not correlate with the density of vibrations at the donor/acceptor excited-state energy gap. Thus, if vibrational-electronic resonances occur in any of these dyads, which seems likely, the impact on the rate of energy transfer is small.