Coherent Control over Nuclear Hyperpolarization Using an Optically Initializable Chromophore-Radical System

Le, Hoang M.; Straub, Joshua S.; Stern, Quentin; Equbal, Asif; Qiu, Yunfan; Krzyaniak, Matthew D.; Wasielewski, Michael R.; Han, Songi

doi:10.1021/jacs.5c07862

Coherent Control over Nuclear Hyperpolarization Using an Optically Initializable Chromophore-Radical System

Journal Article · Wed Sep 17 00:00:00 EDT 2025 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5c07862· OSTI ID:2998548

Le, Hoang M. ^[1]; Straub, Joshua S. ^[1]; Stern, Quentin ^[1]; ^[2]; ^[1]; ^[1]; ^[1]; ^[1]

Northwestern Univ., Evanston, IL (United States)
New York Univ. (NYU), Abu Dhabi (United Arab Emirates)

Chromophore radicals (CR) are emerging as important components for molecular quantum information science (QIS), especially in the context of quantum sensing. Here, we demonstrate that the optically hyperpolarized electrons in a 1,6,7,12-tetrakis(4-tert-butylphenoxy)-perylene-3,4,9,10-bis(dicarboximide) (tpPDI) covalently linked to a partially deuterated 1,3-bis(diphenylene)-d₁₆-2-phenylallyl radical (BDPA-d₁₆) can be coherently manipulated via pulsed dynamic nuclear polarization (DNP) methods to transfer polarization to nuclear spins and back. Under light illumination at 85 K, electron hyperpolarization in BDPA is enhanced 2.1- to 2.4-fold over thermal polarization and lasts for more than 100 ms. By applying nuclear orientation via electron spin-locking (NOVEL) DNP, this optically amplified electron hyperpolarization was successfully transferred to a ¹H nuclear spin within the CR system and efficiently returned to the electron spin for readout via reverse-NOVEL. The NOVEL transfer efficiency of 65% amounts to a 688-fold nuclear spin hyperpolarization of the target nuclear spin, considering the 2.1-fold electron spin hyperpolarization. This reversible coherent manipulation of hyperpolarization transfer highlights the utility of CR systems to initialize and read out nuclear spin states in a disordered matrix at moderate cryogenic temperatures. Coupled with CRs’ environmental compatibility, tunability, and precise state initialization, these results highlight the promising role of nuclear spins in CRs for QIS applications, including quantum sensing and memory.

View Accepted Manuscript (DOE)

Research Organization:: American Chemical Society (ACS-C)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0021314

OSTI ID:: 2998548

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 39 Vol. 147; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (66)

Optical Spin Polarization of a Narrow‐Linewidth Electron‐Spin Qubit in a Chromophore/Stable‐Radical System Qiu, Yunfan; Equbal, Asif; Lin, Chenjian Angewandte Chemie International Edition, Vol. 62, Issue 6 https://doi.org/10.1002/anie.202214668	journal	December 2022
Transient oscillations in pulsed dynamic nuclear polarization van den Heuvel, D. J.; Henstra, A.; Lin, T. -S. Chemical Physics Letters, Vol. 188, Issue 3-4 https://doi.org/10.1016/0009-2614(92)90008-B	journal	January 1992
Enhanced dynamic nuclear polarization by the integrated solid effect Henstra, A.; Dirksen, P.; Wenckebach, W. Th. Physics Letters A, Vol. 134, Issue 2 https://doi.org/10.1016/0375-9601(88)90950-4	journal	December 1988
Quantum computers and quantum coherence DiVincenzo, David P.; Loss, Daniel Journal of Magnetism and Magnetic Materials, Vol. 200, Issue 1-3 https://doi.org/10.1016/S0304-8853(99)00315-7	journal	October 1999
Sample volume effects in optical overhauser dynamic nuclear polarization Cheney, Daniel J.; Wedge, Christopher J. Journal of Magnetic Resonance, Vol. 337 https://doi.org/10.1016/j.jmr.2022.107170	journal	April 2022
Dynamic electron and nuclear spin polarization in solution using porphyrin and tris(2,4,6-trichlorophenyl)-methyl (TTM) radical derivatives Yabuki, Reiya; Nishimura, Koki; Sawada, Yuta Journal of Magnetic Resonance Open, Vol. 22 https://doi.org/10.1016/j.jmro.2024.100181	journal	March 2025
Enhanced Intersystem Crossing and Transient Electron Spin Polarization in a Photoexcited Pentacene–Trityl Radical Avalos, Claudia E.; Richert, Sabine; Socie, Etienne The Journal of Physical Chemistry A, Vol. 124, Issue 29 https://doi.org/10.1021/acs.jpca.0c03498	journal	June 2020
Organic Mixed-Valence Compounds and the Overhauser Effect in Insulating Solids Pylaeva, Svetlana; Marx, Patrick; Singh, Gurjot The Journal of Physical Chemistry A, Vol. 125, Issue 3 https://doi.org/10.1021/acs.jpca.0c11296	journal	January 2021
Spinning-Driven Dynamic Nuclear Polarization with Optical Pumping Kundu, Krishnendu; Dubroca, Thierry; Rane, Vinayak The Journal of Physical Chemistry A, Vol. 126, Issue 16 https://doi.org/10.1021/acs.jpca.2c01559	journal	April 2022
Distance Dependence of Electron Spin Polarization during Photophysical Quenching of Excited Naphthalene by TEMPO Radical Rane, Vinayak; Das, Ranjan The Journal of Physical Chemistry A, Vol. 119, Issue 22 https://doi.org/10.1021/acs.jpca.5b01989	journal	May 2015
Achieving Maximal Enhancement of Electron Spin Polarization in Stable Nitroxyl Radicals at Room Temperature Rane, Vinayak The Journal of Physical Chemistry B, Vol. 125, Issue 21 https://doi.org/10.1021/acs.jpcb.1c03111	journal	May 2021
Optical Initialization of Molecular Qubit Spin States Using Weak Exchange Coupling to Photogenerated Fullerene Triplet States Mao, Haochuan; Young, Ryan M.; Krzyaniak, Matthew D. The Journal of Physical Chemistry B, Vol. 126, Issue 49 https://doi.org/10.1021/acs.jpcb.2c07096	journal	December 2022
Dynamic Electron Polarization Lasting More Than 10 μs by Hybridizing Porphyrin and TEMPO with Flexible Linkers Nishimura, Koki; Yabuki, Reiya; Hamachi, Tomoyuki The Journal of Physical Chemistry B, Vol. 127, Issue 5 https://doi.org/10.1021/acs.jpcb.2c07936	journal	January 2023
Quantitative Structure-Based Prediction of Electron Spin Decoherence in Organic Radicals Canarie, Elizabeth R.; Jahn, Samuel M.; Stoll, Stefan The Journal of Physical Chemistry Letters, Vol. 11, Issue 9 https://doi.org/10.1021/acs.jpclett.0c00768	journal	April 2020
Indirect Detection of the Protons in and around Biradicals and their Mechanistic Role in MAS-DNP Chatterjee, Satyaki; Scott, Faith J.; Sigurdsson, Snorri Th. The Journal of Physical Chemistry Letters, Vol. 16, Issue 2 https://doi.org/10.1021/acs.jpclett.4c03254	journal	January 2025
A Molecular Approach to Quantum Sensing Yu, Chung-Jui; von Kugelgen, Stephen; Laorenza, Daniel W. ACS Central Science, Vol. 7, Issue 5 https://doi.org/10.1021/acscentsci.0c00737	journal	April 2021
Exploring Photogenerated Molecular Quartet States as Spin Qubits and Qudits Mayländer, Maximilian; Chen, Su; Lorenzo, Emmaline R. Journal of the American Chemical Society, Vol. 143, Issue 18 https://doi.org/10.1021/jacs.1c01620	journal	April 2021
Efficient Pulsed Dynamic Nuclear Polarization with the X-Inverse-X Sequence Redrouthu, Venkata SubbaRao; Mathies, Guinevere Journal of the American Chemical Society, Vol. 144, Issue 4 https://doi.org/10.1021/jacs.1c09900	journal	January 2022
Electronic Spin Qubit Candidates Arrayed within Layered Two-Dimensional Polymers Oanta, Alexander K.; Collins, Kelsey A.; Evans, Austin M. Journal of the American Chemical Society, Vol. 145, Issue 1 https://doi.org/10.1021/jacs.2c11784	journal	December 2022
Room Temperature Electron Spin Coherence in Photogenerated Molecular Spin Qubit Candidates Mayländer, Maximilian; Thielert, Philipp; Quintes, Theresia Journal of the American Chemical Society, Vol. 145, Issue 25 https://doi.org/10.1021/jacs.3c04021	journal	June 2023
Enhancing Coherence Times of Chromophore-Radical Molecular Qubits and Qudits by Rational Design Qiu, Yunfan; Eckvahl, Hannah J.; Equbal, Asif Journal of the American Chemical Society, Vol. 145, Issue 47 https://doi.org/10.1021/jacs.3c10772	journal	November 2023
Light-Harvesting Spin Hyperpolarization of Organic Radicals in a Metal–Organic Framework Hamachi, Tomoyuki; Inoue, Miku; Fuki, Masaaki Journal of the American Chemical Society, Vol. 147, Issue 5 https://doi.org/10.1021/jacs.4c14916	journal	January 2025
Scaling Up Electronic Spin Qubits into a Three-Dimensional Metal–Organic Framework Yamabayashi, Tsutomu; Atzori, Matteo; Tesi, Lorenzo Journal of the American Chemical Society, Vol. 140, Issue 38 https://doi.org/10.1021/jacs.8b06733	journal	August 2018
A silicon-based nuclear spin quantum computer Kane, B. E. Nature, Vol. 393, Issue 6681 https://doi.org/10.1038/30156	journal	May 1998
High-fidelity readout and control of a nuclear spin qubit in silicon Pla, Jarryd J.; Tan, Kuan Y.; Dehollain, Juan P. Nature, Vol. 496, Issue 7445 https://doi.org/10.1038/nature12011	journal	April 2013
High-dynamic-range magnetometry with a single nuclear spin in diamond Waldherr, G.; Beck, J.; Neumann, P. Nature Nanotechnology, Vol. 7, Issue 2 https://doi.org/10.1038/nnano.2011.224	journal	December 2011
Storing quantum information for 30 seconds in a nanoelectronic device Muhonen, Juha T.; Dehollain, Juan P.; Laucht, Arne Nature Nanotechnology, Vol. 9, Issue 12 https://doi.org/10.1038/nnano.2014.211	journal	October 2014
High-fidelity transfer and storage of photon states in a single nuclear spin Yang, Sen; Wang, Ya; Rao, D. D. Bhaktavatsala Nature Photonics, Vol. 10, Issue 8 https://doi.org/10.1038/nphoton.2016.103	journal	June 2016
High field magnetometry with hyperpolarized nuclear spins Sahin, Ozgur; de Leon Sanchez, Erica; Conti, Sophie Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-32907-8	journal	September 2022
Nuclear spin assisted magnetic field angle sensing Qiu, Ziwei; Vool, Uri; Hamo, Assaf npj Quantum Information, Vol. 7, Issue 1 https://doi.org/10.1038/s41534-021-00374-6	journal	February 2021
A many-body quantum register for a spin qubit Appel, Martin Hayhurst; Ghorbal, Alexander; Shofer, Noah Nature Physics, Vol. 21, Issue 3 https://doi.org/10.1038/s41567-024-02746-z	journal	January 2025
Properties and applications of photoexcited chromophore–radical systems Quintes, Theresia; Mayländer, Maximilian; Richert, Sabine Nature Reviews Chemistry, Vol. 7, Issue 2 https://doi.org/10.1038/s41570-022-00453-y	journal	January 2023
Reversible spin-optical interface in luminescent organic radicals Gorgon, Sebastian; Lv, Kuo; Grüne, Jeannine Nature, Vol. 620, Issue 7974 https://doi.org/10.1038/s41586-023-06222-1	journal	August 2023
Molecular spin qudits for quantum algorithms Moreno-Pineda, Eufemio; Godfrin, Clément; Balestro, Franck Chemical Society Reviews, Vol. 47, Issue 2 https://doi.org/10.1039/C5CS00933B	journal	January 2018
Optically generated hyperpolarization for sensitivity enhancement in solution-state NMR spectroscopy Dale, Matthew W.; Wedge, Christopher J. Chemical Communications, Vol. 52, Issue 90 https://doi.org/10.1039/C6CC06651H	journal	January 2016
Photo-induced radical polarization and liquid-state dynamic nuclear polarization using fullerene nitroxide derivatives Liu, Guoquan; Liou, Shu-Hao; Enkin, Nikolay Physical Chemistry Chemical Physics, Vol. 19, Issue 47 https://doi.org/10.1039/C7CP06073D	journal	January 2017
Viscosity effects on optically generated electron and nuclear spin hyperpolarization Dale, Matthew W.; Cheney, Daniel J.; Vallotto, Claudio Physical Chemistry Chemical Physics, Vol. 22, Issue 48 https://doi.org/10.1039/D0CP04012F	journal	January 2020
Accessing the triplet state of perylenediimide by radical-enhanced intersystem crossing Mayländer, Maximilian; Nolden, Oliver; Franz, Michael Chemical Science, Vol. 13, Issue 22 https://doi.org/10.1039/D2SC01899C	journal	January 2022
Unravelling the major factors in photo-oxidative stability of anthradithiophene derivatives Thorley, Karl J.; Le, Hoang; Song, Yang Journal of Materials Chemistry C, Vol. 10, Issue 42 https://doi.org/10.1039/D2TC02922G	journal	January 2022
PDI–trityl dyads as photogenerated molecular spin qubit candidates Mayländer, Maximilian; Kopp, Kevin; Nolden, Oliver Chemical Science, Vol. 14, Issue 39 https://doi.org/10.1039/D3SC04375D	journal	January 2023
Nuclear magnetic resonance and dielectric spectroscopy of a simple supercooled liquid: 2-methyl tetrahydrofuran Qi, F.; El Goresy, T.; Böhmer, R. The Journal of Chemical Physics, Vol. 118, Issue 16 https://doi.org/10.1063/1.1563599	journal	April 2003
Electron spin polarization of the excited quartet state of strongly coupled triplet–doublet spin systems Kandrashkin, Yuri; van der Est, Art The Journal of Chemical Physics, Vol. 120, Issue 10 https://doi.org/10.1063/1.1645773	journal	March 2004
A phenomenological scheme for reversed quartet mechanism of electron spin polarization in covalently linked systems of chromophore and free radical: Determination of magnitude of polarization and application to pyrene–TEMPO linked molecules Tripathi, Alok Kumar; Rane, Vinayak; Kundu, Sushma The Journal of Chemical Physics, Vol. 151, Issue 15 https://doi.org/10.1063/1.5124731	journal	October 2019
Dynamic nuclear polarization by two-pulse phase modulation Redrouthu, Venkata SubbaRao; Vinod-Kumar, Sanjay; Mathies, Guinevere The Journal of Chemical Physics, Vol. 159, Issue 1 https://doi.org/10.1063/5.0153053	journal	July 2023
Optimal control design strategies for pulsed dynamic nuclear polarization Carvalho, José P.; Goodwin, David L.; Wili, Nino The Journal of Chemical Physics, Vol. 162, Issue 5 https://doi.org/10.1063/5.0244723	journal	February 2025
Room temperature hyperpolarization of nuclear spins in bulk Tateishi, K.; Negoro, M.; Nishida, S. Proceedings of the National Academy of Sciences, Vol. 111, Issue 21 https://doi.org/10.1073/pnas.1315778111	journal	May 2014
The theory of nuclear orientation via electron spin locking (NOVEL) Henstra, A.; Wenckebach, W. Th. Molecular Physics, Vol. 106, Issue 7 https://doi.org/10.1080/00268970801998262	journal	April 2008
Pulsed EPR study on large dynamic electron polarisation created in the quenching of photo-excited xanthene dyes by nitroxide radicals in aqueous solutions Takahashi, Hirona; Iwama, Masaki; Akai, Nobuyuki Molecular Physics, Vol. 112, Issue 7 https://doi.org/10.1080/00268976.2013.827255	journal	August 2013
Polarization of Nuclei in Metals Overhauser, Albert W. Physical Review, Vol. 92, Issue 2 https://doi.org/10.1103/PhysRev.92.411	journal	October 1953
Stable three-axis nuclear-spin gyroscope in diamond Ajoy, Ashok; Cappellaro, Paola Physical Review A, Vol. 86, Issue 6 https://doi.org/10.1103/PhysRevA.86.062104	journal	December 2012
Rapidly Enhanced Spin-Polarization Injection in an Optically Pumped Spin Ratchet Sarkar, Adrisha; Blankenship, Brian; Druga, Emanuel Physical Review Applied, Vol. 18, Issue 3 https://doi.org/10.1103/PhysRevApplied.18.034079	journal	September 2022
Role of electron polarization in nuclear spin diffusion Chessari, Alessandro; Cousin, Samuel F.; Jannin, Sami Physical Review B, Vol. 107, Issue 22 https://doi.org/10.1103/PhysRevB.107.224429	journal	June 2023
Overcoming the nuclear spin diffusion barrier in dynamic nuclear polarization via electron-electron flip-flop Redrouthu, Venkata SubbaRao; Mannaï, Marwa; Taha, Lina Physical Review B, Vol. 111, Issue 10 https://doi.org/10.1103/PhysRevB.111.104417	journal	March 2025
Quantum theory of spectral-diffusion-induced electron spin decoherence Witzel, W. M.; de Sousa, Rogerio; Das Sarma, S. Physical Review B, Vol. 72, Issue 16 https://doi.org/10.1103/PhysRevB.72.161306	journal	October 2005
Coherence of single spins coupled to a nuclear spin bath of varying density Mizuochi, N.; Neumann, P.; Rempp, F. Physical Review B, Vol. 80, Issue 4 https://doi.org/10.1103/PhysRevB.80.041201	journal	July 2009
Dynamic Nuclear Polarization as Kinetically Constrained Diffusion Karabanov, A.; Wiśniewski, D.; Lesanovsky, I. Physical Review Letters, Vol. 115, Issue 2 https://doi.org/10.1103/PhysRevLett.115.020404	journal	July 2015
Initialization and Readout of Nuclear Spins via a Negatively Charged Silicon-Vacancy Center in Diamond Metsch, Mathias H.; Senkalla, Katharina; Tratzmiller, Benedikt Physical Review Letters, Vol. 122, Issue 19 https://doi.org/10.1103/PhysRevLett.122.190503	journal	May 2019
Robust optical polarization of nuclear spin baths using Hamiltonian engineering of nitrogen-vacancy center quantum dynamics Schwartz, Ilai; Scheuer, Jochen; Tratzmiller, Benedikt Science Advances, Vol. 4, Issue 8 https://doi.org/10.1126/sciadv.aat8978	journal	August 2018
Time-optimized pulsed dynamic nuclear polarization Tan, Kong Ooi; Yang, Chen; Weber, Ralph T. Science Advances, Vol. 5, Issue 1 https://doi.org/10.1126/sciadv.aav6909	journal	January 2019
Optically pumped spin polarization as a probe of many-body thermalization Pagliero, Daniela; Zangara, Pablo R.; Henshaw, Jacob Science Advances, Vol. 6, Issue 18 https://doi.org/10.1126/sciadv.aaz6986	journal	May 2020
Direct observation of hyperpolarization breaking through the spin diffusion barrier Stern, Quentin; Cousin, Samuel François; Mentink-Vigier, Frédéric Science Advances, Vol. 7, Issue 18 https://doi.org/10.1126/sciadv.abf5735	journal	April 2021
Observation of dynamic nuclear polarization echoes Wili, Nino; Nielsen, Anders B.; Carvalho, José P. Science Advances, Vol. 10, Issue 42 https://doi.org/10.1126/sciadv.adr2420	journal	October 2024
Hypershifted spin spectroscopy with dynamic nuclear polarization at 1.4 K Pang, Zhenfeng; Sheberstov, Kirill; Rodin, Bogdan A. Science Advances, Vol. 10, Issue 50 https://doi.org/10.1126/sciadv.adr7160	journal	December 2024
Two-electron two-nucleus effective Hamiltonian and the spin diffusion barrier von Witte, Gevin; Kozerke, Sebastian; Ernst, Matthias Science Advances, Vol. 11, Issue 1 https://doi.org/10.1126/sciadv.adr7168	journal	January 2025
Quantum Register Based on Individual Electronic and Nuclear Spin Qubits in Diamond Dutt, M. V. G.; Childress, L.; Jiang, L. Science, Vol. 316, Issue 5829 https://doi.org/10.1126/science.1139831	journal	June 2007
Reverse dynamic nuclear polarisation for indirect detection of nuclear spins close to unpaired electrons Wili, Nino; Ardenkjær-Larsen, Jan Henrik; Jeschke, Gunnar Magnetic Resonance, Vol. 3, Issue 2 https://doi.org/10.5194/mr-3-161-2022	journal	August 2022

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