Fast photo-driven electron spin coherence transfer

The effect of electron-nuclear hyperfine coupling on coherence dephasing

Matthew D. Krzyaniak, Lukáš Kobr, Brandon K. Rugg, Brian T. Phelan, Eric A. Margulies, Jordan N. Nelson, Ryan M. Young, Michael R Wasielewski

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Selective photoexcitation of the donor in an electron donor-acceptor1-acceptor2 (D-A1-A2) molecule, in which D = perylene and both A1 and A2 = naphthalene-1,8:4,5-bis(dicarboximide), results in sub-nanosecond formation of a spin-correlated singlet radical pair 1(D+•-A1-•-A2) having a large electron spin-spin exchange interaction, 2J, which precludes its observation by transient EPR spectroscopy. Subsequent selective photoexcitation of A1-• rapidly produces 1(D+•-A1-A2-•), resulting in a dramatic decrease in 2J, which allows coherent spin evolution to mix the singlet (S) radical pair state 1(D+•-A1-A2-•) with the T0 triplet sublevel of 3(D+•-A1-A2-•) in an applied magnetic field, where B 蠑 2J. A spin-polarized transient EPR spectrum characteristic of the spin-correlated radical pair D+•-A1-A2-• is then observed. The time delay between the two laser pulses was incremented to measure the rate of decoherence in 1(D+•-A1-•-A2) in toluene at 295 K, which was found to be 8.1 × 107 s-1. Deuteration of the perylene donor or the toluene solvent decreases the decoherence rate constant of 1(D+•-A1-•-A2) to 4.3 × 107 s-1 and 4.6 × 107 s-1, respectively, while deuteration of both the perylene donor and the toluene solvent reduced the decoherence rate constant by more than half to 3.4 × 107 s-1. The data show that decreasing electron-nuclear hyperfine interactions significantly increases the zero quantum coherence lifetime of the spin-correlated radical pair.

Original languageEnglish
Pages (from-to)7962-7967
Number of pages6
JournalJournal of Materials Chemistry C
Volume3
Issue number30
DOIs
Publication statusPublished - Aug 14 2015

Fingerprint

Perylene
Toluene
Photoexcitation
Paramagnetic resonance
Electrons
Rate constants
Exchange interactions
Naphthalene
Laser pulses
Time delay
Spectroscopy
Magnetic fields
Molecules

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Chemistry

Cite this

Fast photo-driven electron spin coherence transfer : The effect of electron-nuclear hyperfine coupling on coherence dephasing. / Krzyaniak, Matthew D.; Kobr, Lukáš; Rugg, Brandon K.; Phelan, Brian T.; Margulies, Eric A.; Nelson, Jordan N.; Young, Ryan M.; Wasielewski, Michael R.

In: Journal of Materials Chemistry C, Vol. 3, No. 30, 14.08.2015, p. 7962-7967.

Research output: Contribution to journalArticle

Krzyaniak, Matthew D. ; Kobr, Lukáš ; Rugg, Brandon K. ; Phelan, Brian T. ; Margulies, Eric A. ; Nelson, Jordan N. ; Young, Ryan M. ; Wasielewski, Michael R. / Fast photo-driven electron spin coherence transfer : The effect of electron-nuclear hyperfine coupling on coherence dephasing. In: Journal of Materials Chemistry C. 2015 ; Vol. 3, No. 30. pp. 7962-7967.
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