Direct Observation of Triplet-Triplet Energy Transfer in DNA between Energy Donor and Acceptor C‑Nucleotides

Investigating the migration of excited-state energy in DNA is crucial for a deep understanding of protection mechanisms and light-induced DNA damage. While numerous reports focused on single electron transfer and Förster-type energy transfer in DNA, studies on the Dexter-type triplet-triplet energy transfer are scarce, in particular, those with direct detection of photoexcited triplet states. Herein, we present direct measurements of the distance-dependent triplet-triplet energy transfer rates through DNA by using transient absorption spectroscopy. This was achieved through the synthetic incorporation of thioxanthone as an energy donor and naphthalene as an energy acceptor into a DNA double strand at defined positions. The energy transfer rates strongly depend on the number of A-T base pairs (up to four) separating the energy donor from the energy acceptor. We observed a fast energy transfer rate with a time constant of 17 ns for the DNA sample in which the donor and acceptor are directly adjacent in the DNA. By analyzing two additional donor-acceptor distances, a steep exponential distance dependence with an attenuation factor of 1.15 Å^-1 could be obtained. Our results demonstrate that DNA acts as a poor conductor of triplet energy when energy donors with triplet energies below 2.7 eV are used, complementing more indirect studies on sensitized DNA damage.