Abstract
Controlling spin-spin interactions in multispin molecular assemblies is important for developing new approaches to quantum information processing. In this work, a covalent electron donor-acceptor-radical triad is used to probe spin-selective reduction of the stable radical to its diamagnetic anion. The molecule consists of a perylene electron donor chromophore (D) bound to a pyromellitimide acceptor (A), which is, in turn, linked to a stable α,γ-bisdiphenylene-β-phenylallyl radical (R•) to produce D-A-R•. Selective photoexcitation of D within D-A-R• results in ultrafast electron transfer to form the D+•-A-•-R• triradical, where D+•-A-• is a singlet spin-correlated radical pair (SCRP), in which both SCRP spins are uncorrelated relative to the R• spin. Subsequent ultrafast electron transfer within the triradical forms D+•-A-R-, but its yield is controlled by spin statistics of the uncorrelated A-•-R• radical pair, where the initial charge separation yields a 3:1 statistical mixture of D+•-3(A-•-R•) and D+•-1(A-•-R•), and subsequent reduction of R• only occurs in D+•-1(A-•-R•). These findings inform the design of multispin systems to transfer spin coherence between molecules targeting quantum information processing using the agency of SCRPs.
| Original language | English |
|---|---|
| Pages (from-to) | 15660-15663 |
| Number of pages | 4 |
| Journal | Journal of the American Chemical Society |
| Volume | 139 |
| Issue number | 44 |
| DOIs | |
| Publication status | Published - Nov 8 2017 |
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ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Spin-Selective Photoreduction of a Stable Radical within a Covalent Donor-Acceptor-Radical Triad. / Rugg, Brandon K.; Phelan, Brian T.; Horwitz, Noah E.; Young, Ryan M.; Krzyaniak, Matthew D.; Ratner, Mark A; Wasielewski, Michael R.
In: Journal of the American Chemical Society, Vol. 139, No. 44, 08.11.2017, p. 15660-15663.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Spin-Selective Photoreduction of a Stable Radical within a Covalent Donor-Acceptor-Radical Triad
AU - Rugg, Brandon K.
AU - Phelan, Brian T.
AU - Horwitz, Noah E.
AU - Young, Ryan M.
AU - Krzyaniak, Matthew D.
AU - Ratner, Mark A
AU - Wasielewski, Michael R
PY - 2017/11/8
Y1 - 2017/11/8
N2 - Controlling spin-spin interactions in multispin molecular assemblies is important for developing new approaches to quantum information processing. In this work, a covalent electron donor-acceptor-radical triad is used to probe spin-selective reduction of the stable radical to its diamagnetic anion. The molecule consists of a perylene electron donor chromophore (D) bound to a pyromellitimide acceptor (A), which is, in turn, linked to a stable α,γ-bisdiphenylene-β-phenylallyl radical (R•) to produce D-A-R•. Selective photoexcitation of D within D-A-R• results in ultrafast electron transfer to form the D+•-A-•-R• triradical, where D+•-A-• is a singlet spin-correlated radical pair (SCRP), in which both SCRP spins are uncorrelated relative to the R• spin. Subsequent ultrafast electron transfer within the triradical forms D+•-A-R-, but its yield is controlled by spin statistics of the uncorrelated A-•-R• radical pair, where the initial charge separation yields a 3:1 statistical mixture of D+•-3(A-•-R•) and D+•-1(A-•-R•), and subsequent reduction of R• only occurs in D+•-1(A-•-R•). These findings inform the design of multispin systems to transfer spin coherence between molecules targeting quantum information processing using the agency of SCRPs.
AB - Controlling spin-spin interactions in multispin molecular assemblies is important for developing new approaches to quantum information processing. In this work, a covalent electron donor-acceptor-radical triad is used to probe spin-selective reduction of the stable radical to its diamagnetic anion. The molecule consists of a perylene electron donor chromophore (D) bound to a pyromellitimide acceptor (A), which is, in turn, linked to a stable α,γ-bisdiphenylene-β-phenylallyl radical (R•) to produce D-A-R•. Selective photoexcitation of D within D-A-R• results in ultrafast electron transfer to form the D+•-A-•-R• triradical, where D+•-A-• is a singlet spin-correlated radical pair (SCRP), in which both SCRP spins are uncorrelated relative to the R• spin. Subsequent ultrafast electron transfer within the triradical forms D+•-A-R-, but its yield is controlled by spin statistics of the uncorrelated A-•-R• radical pair, where the initial charge separation yields a 3:1 statistical mixture of D+•-3(A-•-R•) and D+•-1(A-•-R•), and subsequent reduction of R• only occurs in D+•-1(A-•-R•). These findings inform the design of multispin systems to transfer spin coherence between molecules targeting quantum information processing using the agency of SCRPs.
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U2 - 10.1021/jacs.7b10458
DO - 10.1021/jacs.7b10458
M3 - Article
VL - 139
SP - 15660
EP - 15663
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 44
ER -