Detecting Chirality-Induced Spin Selectivity in Randomly Oriented Radical Pairs Photogenerated by Hole Transfer

Hannah J. Eckvahl; Graeme Copley; Ryan M. Young; Matthew D. Krzyaniak; Michael R. Wasielewski

doi:10.1021/jacs.4c08706

Detecting Chirality-Induced Spin Selectivity in Randomly Oriented Radical Pairs Photogenerated by Hole Transfer

Hannah J. Eckvahl, Graeme Copley, Ryan M. Young, Matthew D. Krzyaniak^*, Michael R. Wasielewski^*

^*Corresponding author for this work

Paula M. Trienens Institute for Sustainability and Energy

Research output: Contribution to journal › Article › peer-review

Abstract

Chirality-induced spin selectivity (CISS) has the potential to control the spin dynamics of chiral molecules for applications in quantum information science. Here we investigate the effect of CISS on the spin dynamics of radical pair formation following photodriven hole transfer in a pair of donor-chiral bridge-acceptor (D-Bχ-A) enantiomers, where D = 2,2,6,6-tetramethyl[1,3]-dioxolo[4,5-f][1,3]benzodioxole, Bχ = (R)- or (S)-2,2′-dimethoxy-4,4′-diphenyl-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthalene, and A = naphthalene-(1,4:5,8)-bis(dicarboximide). The results are compared to those obtained on the corresponding achiral D-B-A reference molecule in which B = 2″,3′,5′,6″-tetramethyl-1,1′:4′,1″:4″,1‴-quaterphenyl. Photoexcitation of A in a randomly oriented sample of D-Bχ-A in glassy butyronitrile at 85 K results in subnanosecond two-step hole transfer from ¹*A to D to form D^•+-Bχ-A^•-, which was characterized using time-resolved electron paramagnetic resonance (TREPR) spectroscopy at X (9.6 GHz), Q (34 GHz), and W (94 GHz) bands. The spectra show line shape changes that are characteristic of a ∼38% contribution of CISS to the spin dynamics of D^•+-Bχ-A^•- formation. The line shape changes resulting from CISS are particularly apparent in the TREPR spectra at X-band as predicted by recent theory. These results show that (1) CISS has a significant influence on radical pair dynamics initiated by photodriven hole transfer, which is complementary to our recent electron transfer results, and (2) CISS can be detected using TREPR on radical pairs that are randomly oriented relative to an external magnetic field.

Original language	English (US)
Pages (from-to)	24125-24132
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	146
Issue number	34
DOIs	https://doi.org/10.1021/jacs.4c08706
State	Published - Aug 28 2024

Funding

The authors are grateful to Yizhe Chen and Colin Tichvon for their contributions to the synthesis and characterization in this work. The work was funded by the Horizon Europe Program within the ERC-Synergy project CASTLE project no. 101071533 (M.R.W.). Research supported as part of the Center for Molecular Quantum Transduction, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under award DE-SC0021314 (M.D.K.), H nuclear magnetic resonance (NMR) spectroscopy, and mass spectrometry are conducted in IMSERC facilities at Northwestern University, which have received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), NSF CHE-1048773, Northwestern University, the State of Illinois, and the International Institute for Nanotechnology (IIN).

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.4c08706

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@article{3e4656a37e9c459baf573d043089bb16,

title = "Detecting Chirality-Induced Spin Selectivity in Randomly Oriented Radical Pairs Photogenerated by Hole Transfer",

abstract = "Chirality-induced spin selectivity (CISS) has the potential to control the spin dynamics of chiral molecules for applications in quantum information science. Here we investigate the effect of CISS on the spin dynamics of radical pair formation following photodriven hole transfer in a pair of donor-chiral bridge-acceptor (D-Bχ-A) enantiomers, where D = 2,2,6,6-tetramethyl[1,3]-dioxolo[4,5-f][1,3]benzodioxole, Bχ = (R)- or (S)-2,2′-dimethoxy-4,4′-diphenyl-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthalene, and A = naphthalene-(1,4:5,8)-bis(dicarboximide). The results are compared to those obtained on the corresponding achiral D-B-A reference molecule in which B = 2″,3′,5′,6″-tetramethyl-1,1′:4′,1″:4″,1‴-quaterphenyl. Photoexcitation of A in a randomly oriented sample of D-Bχ-A in glassy butyronitrile at 85 K results in subnanosecond two-step hole transfer from 1*A to D to form D•+-Bχ-A•-, which was characterized using time-resolved electron paramagnetic resonance (TREPR) spectroscopy at X (9.6 GHz), Q (34 GHz), and W (94 GHz) bands. The spectra show line shape changes that are characteristic of a ∼38% contribution of CISS to the spin dynamics of D•+-Bχ-A•- formation. The line shape changes resulting from CISS are particularly apparent in the TREPR spectra at X-band as predicted by recent theory. These results show that (1) CISS has a significant influence on radical pair dynamics initiated by photodriven hole transfer, which is complementary to our recent electron transfer results, and (2) CISS can be detected using TREPR on radical pairs that are randomly oriented relative to an external magnetic field.",

author = "Eckvahl, {Hannah J.} and Graeme Copley and Young, {Ryan M.} and Krzyaniak, {Matthew D.} and Wasielewski, {Michael R.}",

note = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society.",

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doi = "10.1021/jacs.4c08706",

language = "English (US)",

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T1 - Detecting Chirality-Induced Spin Selectivity in Randomly Oriented Radical Pairs Photogenerated by Hole Transfer

AU - Eckvahl, Hannah J.

AU - Copley, Graeme

AU - Young, Ryan M.

AU - Krzyaniak, Matthew D.

AU - Wasielewski, Michael R.

PY - 2024/8/28

Y1 - 2024/8/28

N2 - Chirality-induced spin selectivity (CISS) has the potential to control the spin dynamics of chiral molecules for applications in quantum information science. Here we investigate the effect of CISS on the spin dynamics of radical pair formation following photodriven hole transfer in a pair of donor-chiral bridge-acceptor (D-Bχ-A) enantiomers, where D = 2,2,6,6-tetramethyl[1,3]-dioxolo[4,5-f][1,3]benzodioxole, Bχ = (R)- or (S)-2,2′-dimethoxy-4,4′-diphenyl-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthalene, and A = naphthalene-(1,4:5,8)-bis(dicarboximide). The results are compared to those obtained on the corresponding achiral D-B-A reference molecule in which B = 2″,3′,5′,6″-tetramethyl-1,1′:4′,1″:4″,1‴-quaterphenyl. Photoexcitation of A in a randomly oriented sample of D-Bχ-A in glassy butyronitrile at 85 K results in subnanosecond two-step hole transfer from 1*A to D to form D•+-Bχ-A•-, which was characterized using time-resolved electron paramagnetic resonance (TREPR) spectroscopy at X (9.6 GHz), Q (34 GHz), and W (94 GHz) bands. The spectra show line shape changes that are characteristic of a ∼38% contribution of CISS to the spin dynamics of D•+-Bχ-A•- formation. The line shape changes resulting from CISS are particularly apparent in the TREPR spectra at X-band as predicted by recent theory. These results show that (1) CISS has a significant influence on radical pair dynamics initiated by photodriven hole transfer, which is complementary to our recent electron transfer results, and (2) CISS can be detected using TREPR on radical pairs that are randomly oriented relative to an external magnetic field.

AB - Chirality-induced spin selectivity (CISS) has the potential to control the spin dynamics of chiral molecules for applications in quantum information science. Here we investigate the effect of CISS on the spin dynamics of radical pair formation following photodriven hole transfer in a pair of donor-chiral bridge-acceptor (D-Bχ-A) enantiomers, where D = 2,2,6,6-tetramethyl[1,3]-dioxolo[4,5-f][1,3]benzodioxole, Bχ = (R)- or (S)-2,2′-dimethoxy-4,4′-diphenyl-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthalene, and A = naphthalene-(1,4:5,8)-bis(dicarboximide). The results are compared to those obtained on the corresponding achiral D-B-A reference molecule in which B = 2″,3′,5′,6″-tetramethyl-1,1′:4′,1″:4″,1‴-quaterphenyl. Photoexcitation of A in a randomly oriented sample of D-Bχ-A in glassy butyronitrile at 85 K results in subnanosecond two-step hole transfer from 1*A to D to form D•+-Bχ-A•-, which was characterized using time-resolved electron paramagnetic resonance (TREPR) spectroscopy at X (9.6 GHz), Q (34 GHz), and W (94 GHz) bands. The spectra show line shape changes that are characteristic of a ∼38% contribution of CISS to the spin dynamics of D•+-Bχ-A•- formation. The line shape changes resulting from CISS are particularly apparent in the TREPR spectra at X-band as predicted by recent theory. These results show that (1) CISS has a significant influence on radical pair dynamics initiated by photodriven hole transfer, which is complementary to our recent electron transfer results, and (2) CISS can be detected using TREPR on radical pairs that are randomly oriented relative to an external magnetic field.

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Detecting Chirality-Induced Spin Selectivity in Randomly Oriented Radical Pairs Photogenerated by Hole Transfer

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