Direct observation of the preference of hole transfer over electron transfer for radical ion pair recombination in donor-bridge-acceptor molecules

Zachary E.X. Dance, Michael J. Ahrens, Amy M. Vega, Annie Butler Ricks, David W. McCamant, Mark A. Ratner, Michael R. Wasielewski

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61 Citations (Scopus)


Understanding how the electronic structures of electron donor-bridge-acceptor (D-B-A) molecules influence the lifetimes of radical ion pairs (RPs) photogenerated within them (D+•-B-A-•) is critical to designing and developing molecular systems for solar energy conversion. A general question that often arises is whether the HOMOs or LUMOs of D, B, and A within D+•-B-A-• are primarily involved in charge recombination. We have developed a new series of D-B-A molecules consisting of a 3,5-dimethyl-4-(9-anthracenyl)julolidine (DMJ-An) electron donor linked to a naphthalene-1,8:4,5-bis(dicarboximide) (NI) acceptor via a series of Phn oligomers, where n = 1-4, to give DMJ-An-Phn-NI. The photoexcited charge transfer state of DMJ-An acts as a high-potential photoreductant to rapidly and nearly quantitatively transfer an electron across the Phn bridge to produce a spin-coherent singlet RP 1(DMJ+•-An-Phn-NI-•). Subsequent radical pair intersystem crossing yields 3(DMJ+•-An-Phn-NI-•). Charge recombination within the triplet RP then gives the neutral triplet state. Time-resolved EPR spectroscopy shows directly that charge recombination of the RP initially produces a spin-polarized triplet state, DMJ-An-Phn-3*NI, that can only be produced by hole transfer involving the HOMOs of D, B, and A within the D-B-A system. After the initial formation of DMJ-An-Phn-3*NI, triplet-triplet energy transfer occurs to produce DMJ-3*An-Phn-NI with rate constants that show a distance dependence consistent with those determined for charge separation and recombination.

Original languageEnglish
Pages (from-to)830-832
Number of pages3
JournalJournal of the American Chemical Society
Issue number3
Publication statusPublished - Jan 23 2008


ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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