Photoinduced Magnetic Exchange-Jump Promotes Ground State Biradical Electron Spin Polarization

Kirk, Martin L.; Shultz, David A.; Marri, Anil Reddy; van der Est, Art

doi:10.1021/jacs.4c00930

Title: Photoinduced Magnetic Exchange-Jump Promotes Ground State Biradical Electron Spin Polarization

Journal Article · 21 March 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.4c00930 · OSTI ID:2337788

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University of New Mexico, Albuquerque, NM (United States); Dept. Chemistry, NC State University
North Carolina State University, Raleigh, NC (United States)
Brock University, Ontario (Canada)

Photoinduced electron spin polarization (ESP) is reported in the electronic ground states of three Pt(II) complexes that are comprised of two S = ½ nitronyl nitroxide (NN) radicals attached through different length para-phenylethynyl bridges to the 3,6 positions of a catecholate (CAT, donor) and 4,4’-di-tert-butyl-2,2’-bipyridine (bpy, acceptor). Complexes 1-3 have from 17 to 41 bonds separating NN radicals, and display cw-EPR spectra consistent with |J_NN-NN| >> |a_N|, |J_NN-NN| ≥ |a_N|, and |J_NN-NN| < |a_N|, respectively, where J_NN-NN is the magnetic exchange coupling between NN radicals in the electronic ground state, and a_N is the isotropic ¹⁴N hyperfine coupling constant. Light-induced transient EPR spectra characterized as enhanced ground-state absorption were observed for all three complexes using 532 nm pulsed laser excitation into the ligand-to-ligand charge transfer (LL’CT) band of the (CAT)Pt(bpy) chromophore. The magnitude of the observed ESP increases in the order 1 < 2 < 3 and is inversely correlated with the magnitude of ground-state J_NN-NN. In addition to the experimental observation net absorptive polarization in 1-3, light excitation also produces multiplet polarization in 2. Since the weak dipolar coupling leads to strong spectral overlap of the absorptive and emissive components, the multiplet polarization is not observed in 1 and 3 and is very weak in 2. Here, the ability to spin polarize multiple radical spins with a single photon is anticipated to advance new photoinduced multi qubit/qudit ESP protocols for quantum information science applications.

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Research Organization:: North Carolina State University, Raleigh, NC (United States)

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

Grant/Contract Number:: SC0024280

OSTI ID:: 2337788

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 13 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (58)

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
Light-driven spin chemistry for quantum information science Wasielewski, Michael R. Physics Today, Vol. 76, Issue 3 https://doi.org/10.1063/PT.3.5196	journal	March 2023
Controlled coherent dynamics of [VO(TPP)], a prototype molecular nuclear qudit with an electronic ancilla Chicco, Simone; Chiesa, Alessandro; Allodi, Giuseppe Chemical Science, Vol. 12, Issue 36 https://doi.org/10.1039/D1SC01358K	journal	January 2021
Calculation of exchange couplings in the electronically excited state of molecular three-spin systems Franz, Michael; Neese, Frank; Richert, Sabine Chemical Science, Vol. 13, Issue 42 https://doi.org/10.1039/D2SC04701B	journal	January 2022
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
Ground State Nuclear Magnetic Resonance Chemical Shifts Predict Charge-Separated Excited State Lifetimes Yang, Jing; Kersi, Dominic K.; Richers, Casseday P. Inorganic Chemistry, Vol. 57, Issue 21 https://doi.org/10.1021/acs.inorgchem.8b02087	journal	October 2018
Excited State Magnetic Exchange Interactions Enable Large Spin Polarization Effects Stein, Benjamin W.; Tichnell, Christopher R.; Chen, Ju Journal of the American Chemical Society, Vol. 140, Issue 6 https://doi.org/10.1021/jacs.7b11397	journal	February 2018
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
Exchange Spin Coupling in Optically Excited States Steenbock, Torben; Rybakowski, Lawrence L. M.; Benner, Dominik Journal of Chemical Theory and Computation, Vol. 18, Issue 8 https://doi.org/10.1021/acs.jctc.2c00256	journal	July 2022
Intramolecular Spin Alignment Utilizing the Excited Molecular Field between the Triplet ( S = 1) Excited State and the Dangling Stable Radicals ( S = 1/2) as Studied by Time-Resolved Electron Spin Resonance: Observation of the Excited Quartet ( S = 3/2) and Quintet ( S = 2) States on the Purely Organic π-Conjugated Spin Systems Teki, Yoshio; Miyamoto, Sadaharu; Iimura, Koji Journal of the American Chemical Society, Vol. 122, Issue 5 https://doi.org/10.1021/ja993151e	journal	February 2000
Photogenerated Spin-Correlated Radical Pairs: From Photosynthetic Energy Transduction to Quantum Information Science Harvey, Samantha M.; Wasielewski, Michael R. Journal of the American Chemical Society, Vol. 143, Issue 38 https://doi.org/10.1021/jacs.1c07706	journal	September 2021
Chromophore-radical excited state antiferromagnetic exchange controls the sign of photoinduced ground state spin polarization Kirk, Martin L.; Shultz, David A.; Hewitt, Patrick Chemical Science, Vol. 12, Issue 41 https://doi.org/10.1039/D1SC02965G	journal	January 2021
A slow relaxing species for molecular spin devices: EPR characterization of static and dynamic magnetic properties of a nitronyl nitroxide radical Collauto, A.; Mannini, M.; Sorace, L. Journal of Materials Chemistry, Vol. 22, Issue 41 https://doi.org/10.1039/c2jm35076a	journal	January 2012
Metal Ion Control of Photoinduced Electron Spin Polarization in Electronic Ground States Kirk, Martin L.; Shultz, David A.; Chen, Ju Journal of the American Chemical Society, Vol. 143, Issue 28 https://doi.org/10.1021/jacs.1c04149	journal	July 2021
Intersystem crossing driven by vibronic spin–orbit coupling: a case study on psoralen Tatchen, Jörg; Gilka, Natalie; Marian, Christel M. Physical Chemistry Chemical Physics, Vol. 9, Issue 38 https://doi.org/10.1039/b706410a	journal	January 2007
Bulk Spin-Resonance Quantum Computation Gershenfeld, N. A.; Chuang, I. L. Science, Vol. 275, Issue 5298 https://doi.org/10.1126/science.275.5298.350	journal	January 1997
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
Recent Innovations in Solid-State and Molecular Qubits for Quantum Information Applications Lavroff, Robert H.; Pennington, Doran L.; Hua, Ash Sueh The Journal of Physical Chemistry B, Vol. 125, Issue 44 https://doi.org/10.1021/acs.jpcb.1c08679	journal	November 2021
Enhanced Intersystem Crossing due to Resonant Energy Transfer to a Remote Spin Kandrashkin, Yuri E.; van der Est, Art The Journal of Physical Chemistry Letters, Vol. 12, Issue 30 https://doi.org/10.1021/acs.jpclett.1c02032	journal	July 2021
A molecular perspective on quantum information Scholes, Gregory D. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 479, Issue 2279 https://doi.org/10.1098/rspa.2023.0599	journal	November 2023
Competitive reversed quartet mechanisms for photogenerated ground state electron spin polarization Kirk, Martin L.; Shultz, David A.; Hewitt, Patrick Chemical Science, Vol. 14, Issue 36 https://doi.org/10.1039/D3SC03049K	journal	January 2023
The Physical Implementation of Quantum Computation DiVincenzo, David P. Fortschritte der Physik, Vol. 48, Issue 9-11 https://doi.org/10.1002/1521-3978(200009)48:9/11<771::aid-prop771>3.0.co;2-e	journal	September 2000
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
Fast Photodriven Electron Spin Coherence Transfer: A Quantum Gate Based on a Spin Exchange J -Jump Kobr, Lukáš; Gardner, Daniel M.; Smeigh, Amanda L. Journal of the American Chemical Society, Vol. 134, Issue 30 https://doi.org/10.1021/ja305650x	journal	July 2012
Time-Resolved Electron Paramagnetic Resonance Spectroscopy Forbes, Malcolm D. E.; Jarocha, Lauren E.; Sim, SooYeon Advances in Physical Organic Chemistry, Vol. 47, p. 1-83 https://doi.org/10.1016/B978-0-12-407754-6.00001-6	book	November 2013
Electron Spin Polarization Transfer from Photogenerated Spin-Correlated Radical Pairs to a Stable Radical Observer Spin Colvin, Michael T.; Carmieli, Raanan; Miura, Tomoaki The Journal of Physical Chemistry A, Vol. 117, Issue 25 https://doi.org/10.1021/jp4045012	journal	June 2013
Evaluation of the β Value of the Phenylene Ethynylene Unit by Probing the Exchange Interaction between Two Nitronyl Nitroxides Shinomiya, Masataka; Higashiguchi, Kenji; Matsuda, Kenji The Journal of Organic Chemistry, Vol. 78, Issue 18 https://doi.org/10.1021/jo4015062	journal	September 2013
Electron Spin Resonance Spectroscopy of Organic Radicals Gerson, Fabian; Huber, Walter https://doi.org/10.1002/3527601627	book	July 2003
π-Topology and Spin Alignment Utilizing the Excited Molecular Field: Observation of the Excited High-Spin Quartet ( S = 3/2) and Quintet ( S = 2) States on Purely Organic π-Conjugated Spin Systems Teki, Yoshio; Miyamoto, Sadaharu; Nakatsuji, Masaaki Journal of the American Chemical Society, Vol. 123, Issue 2 https://doi.org/10.1021/ja001920k	journal	January 2001
Molecular qubits based on photogenerated spin-correlated radical pairs for quantum sensing Mani, Tomoyasu Chemical Physics Reviews, Vol. 3, Issue 2 https://doi.org/10.1063/5.0084072	journal	June 2022
A proposal for using molecular spin qudits as quantum simulators of light–matter interactions Tacchino, F.; Chiesa, A.; Sessoli, R. Journal of Materials Chemistry C, Vol. 9, Issue 32 https://doi.org/10.1039/D1TC00851J	journal	January 2021
Molecular Control of Triplet-Pair Spin Polarization and Its Optoelectronic Magnetic Resonance Probes Reid, Obadiah G.; Johnson, Justin C.; Eaves, Joel D. Accounts of Chemical Research, Vol. 57, Issue 1 https://doi.org/10.1021/acs.accounts.3c00556	journal	December 2023
Single-Photon-Induced Electron Spin Polarization of Two Exchange-Coupled Stable Radicals Kirk, Martin L.; Shultz, David A.; Marri, Anil Reddy Journal of the American Chemical Society, Vol. 144, Issue 46 https://doi.org/10.1021/jacs.2c09680	journal	November 2022
Ensemble quantum computing by NMR spectroscopy Cory, D. G.; Fahmy, A. F.; Havel, T. F. Proceedings of the National Academy of Sciences, Vol. 94, Issue 5 https://doi.org/10.1073/pnas.94.5.1634	journal	March 1997
Hyperfine Interaction, Spin Polarization, and Spin Delocalization as Probes of Donor−Bridge−Acceptor Interactions in Exchange-Coupled Biradicals Kirk, Martin L.; Shultz, David A.; Habel-Rodriguez, Diana The Journal of Physical Chemistry B, Vol. 114, Issue 45 https://doi.org/10.1021/jp102955j	journal	June 2010
Harnessing Electron Spin Hyperpolarization in Chromophore–Radical Spin Probes for Subcellular Resolution in Electron Paramagnetic Resonance Imaging: Concept and Feasibility Rane, Vinayak The Journal of Physical Chemistry B, Vol. 126, Issue 14 https://doi.org/10.1021/acs.jpcb.1c10920	journal	March 2022
Electron Spin Polarization of Functionalized Fullerenes. Reversed Quartet Mechanism Rozenshtein, Vladimir; Berg, Alexander; Stavitski, Eli The Journal of Physical Chemistry A, Vol. 109, Issue 49 https://doi.org/10.1021/jp0540104	journal	November 2005
Ultrafast Intersystem Crossing and Spin Dynamics of Photoexcited Perylene-3,4:9,10-bis(dicarboximide) Covalently Linked to a Nitroxide Radical at Fixed Distances Giacobbe, Emilie M.; Mi, Qixi; Colvin, Michael T. Journal of the American Chemical Society, Vol. 131, Issue 10 https://doi.org/10.1021/ja808924f	journal	March 2009
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
Could the Quantum Internet Be Comprised of Molecular Spins with Tunable Optical Interfaces? Laorenza, Daniel W.; Freedman, Danna E. Journal of the American Chemical Society, Vol. 144, Issue 48 https://doi.org/10.1021/jacs.2c07775	journal	November 2022
Exploiting chemistry and molecular systems for quantum information science Wasielewski, Michael R.; Forbes, Malcolm D. E.; Frank, Natia L. Nature Reviews Chemistry, Vol. 4, Issue 9 https://doi.org/10.1038/s41570-020-0200-5	journal	July 2020
Excited State Exchange Control of Photoinduced Electron Spin Polarization in Electronic Ground States Kirk, Martin L.; Shultz, David A.; Hewitt, Patrick The Journal of Physical Chemistry Letters, Vol. 13, Issue 3 https://doi.org/10.1021/acs.jpclett.1c03491	journal	January 2022
A Synthetic Two-Spin Quantum Bit: g -Engineered Exchange-Coupled Biradical Designed for Controlled-NOT Gate Operations Nakazawa, Shigeaki; Nishida, Shinsuke; Ise, Tomoaki Angewandte Chemie International Edition, Vol. 51, Issue 39 https://doi.org/10.1002/anie.201204489	journal	August 2012
Wave Function Control of Charge-Separated Excited-State Lifetimes Tichnell, Christopher R.; Daley, David R.; Stein, Benjamin W. Journal of the American Chemical Society, Vol. 141, Issue 9 https://doi.org/10.1021/jacs.8b13011	journal	February 2019
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
Photochemically Induced Dynamic Nuclear Polarization in the Solid-State 15N Spectra of Reaction Centers from Photosynthetic Bacteria Rhodobacter sphaeroides R-26 Zysmilich, Martin G.; McDermott, Ann Journal of the American Chemical Society, Vol. 116, Issue 18 https://doi.org/10.1021/ja00097a052	journal	September 1994
Efficient Radical‐Enhanced Intersystem Crossing in an NDI‐TEMPO Dyad: Photophysics, Electron Spin Polarization, and Application in Photodynamic Therapy Wang, Zhijia; Gao, Yuting; Hussain, Mushraf Chemistry – A European Journal, Vol. 24, Issue 70 https://doi.org/10.1002/chem.201804212	journal	November 2018
Excited State Magneto-Structural Correlations Related to Photoinduced Electron Spin Polarization Kirk, Martin L.; Shultz, David A.; Hewitt, Patrick Journal of the American Chemical Society, Vol. 144, Issue 28 https://doi.org/10.1021/jacs.2c03490	journal	July 2022
Electron Transfer in Cyanobacterial Photosystem I Xu, Wu; Chitnis, Parag; Valieva, Alfia Journal of Biological Chemistry, Vol. 278, Issue 30 https://doi.org/10.1074/jbc.M302962200	journal	July 2003
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
Electron Spin Polarization Transfer to the Charge-Separated State from Locally Excited Triplet Configuration: Theory and Its Application to Characterization of Geometry and Electronic Coupling in the Electron Donor−Acceptor System ^† Kobori, Yasuhiro; Fuki, Masaaki; Murai, Hisao The Journal of Physical Chemistry B, Vol. 114, Issue 45 https://doi.org/10.1021/jp102330a	journal	November 2010
Origin of Ferromagnetic Exchange Coupling in Donor–Acceptor Biradical Analogues of Charge-Separated Excited States Chen, Ju; Yang, Jing; Yadav, Munendra Inorganic Chemistry, Vol. 62, Issue 2 https://doi.org/10.1021/acs.inorgchem.2c02903	journal	January 2023
The Second Quantum Revolution: Role and Challenges of Molecular Chemistry Atzori, Matteo; Sessoli, Roberta Journal of the American Chemical Society, Vol. 141, Issue 29 https://doi.org/10.1021/jacs.9b00984	journal	June 2019
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
Excited‐State Dynamics of Non‐Luminescent and Luminescent π‐Radicals Teki, Yoshio Chemistry – A European Journal, Vol. 26, Issue 5 https://doi.org/10.1002/chem.201903444	journal	September 2019
Electron Spin Resonance Wertz, John E.; Bolton, James R. https://doi.org/10.1007/978-94-009-4075-8	book	January 1986
Light-induced electron spin polarization in rigidly linked, strongly coupled triplet–doublet spin pairs Kandrashkin, Yuri; van der Est, Art Chemical Physics Letters, Vol. 379, Issue 5-6 https://doi.org/10.1016/j.cplett.2003.08.073	journal	October 2003
Mechanistic Study of Electron Spin Polarization Transfer in Covalent Donor–Acceptor-Radical Systems Huang, Yuheng; Krzyaniak, Matthew D.; Young, Ryan M. Applied Magnetic Resonance, Vol. 53, Issue 7-9 https://doi.org/10.1007/s00723-021-01402-6	journal	August 2021

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Title: Photoinduced Magnetic Exchange-Jump Promotes Ground State Biradical Electron Spin Polarization

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