Magnetic field-induced switching of the radical-pair intersystem crossing mechanism in a donor-bridge-acceptor molecule for artificial photosynthesis

Michael T. Colvin, Annie Butler Ricks, Amy M. Scott, Amanda Smeigh, Raanan Carmieli, Tomoaki Miura, Michael R. Wasielewski

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

A covalent, fixed-distance donor-bridge-acceptor (D-B-A) molecule was synthesized that upon photoexcitation undergoes ultrafast charge separation to yield a radical ion pair (RP) in which the spin-spin exchange interaction (2J) between the two radicals is sufficiently large to result in preferential RP intersystem crossing to the highest-energy RP eigenstate (T+1) at the 350 mT magnetic field characteristic of X-band (9.5 GHz) EPR spectroscopy. This behavior is unprecedented in covalent D-B-A molecules, and is evidenced by the time-resolved EPR (TREPR) spectrum at X-band of 3*D-B-A derived from RP recombination, which shows all six canonical EPR transitions polarized in emission (e,e,e,e,e,e). In contrast, when the RP is photogenerated in a 3400 mT magnetic field, the TREPR triplet spectrum at W-band (94 GHz) of 3*D-B-A displays the (a,e,e,a,a,e) polarization pattern characteristic of a weakly coupled RP precursor, similar to that observed in photosynthetic reaction center proteins, and indicates a switch to selective population of the lower-energy T0 eigenstate.

Original languageEnglish
Pages (from-to)1240-1243
Number of pages4
JournalJournal of the American Chemical Society
Volume133
Issue number5
DOIs
Publication statusPublished - Feb 9 2011

ASJC Scopus subject areas

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

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