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Metalated Porphyrin Stable Free Radicals: Exploration of Electron Spin Communication and Dynamics

  • Norbert Grzegorzek
    Norbert Grzegorzek
    Institute für Organische Chemie, University of Tübingen, Auf Der Morgenstelle 18, A-Bau, Tübingen 72076, Germany
  • Haochuan Mao
    Haochuan Mao
    Department of Chemistry and Institute for Sustainability and Energy at Northwestern, Northwestern University, Evanston, Illinois 60208-3113, United States
    More by Haochuan Mao
  • Patrick Michel
    Patrick Michel
    Institute für Organische Chemie, University of Tübingen, Auf Der Morgenstelle 18, A-Bau, Tübingen 72076, Germany
  • Marc J. Junge
    Marc J. Junge
    Institute für Organische Chemie, University of Tübingen, Auf Der Morgenstelle 18, A-Bau, Tübingen 72076, Germany
  • Emmaline R. Lorenzo
    Emmaline R. Lorenzo
    Department of Chemistry and Institute for Sustainability and Energy at Northwestern, Northwestern University, Evanston, Illinois 60208-3113, United States
  • Ryan M. Young
    Ryan M. Young
    Department of Chemistry and Institute for Sustainability and Energy at Northwestern, Northwestern University, Evanston, Illinois 60208-3113, United States
  • Matthew D. Krzyaniak
    Matthew D. Krzyaniak
    Department of Chemistry and Institute for Sustainability and Energy at Northwestern, Northwestern University, Evanston, Illinois 60208-3113, United States
  • Michael R. Wasielewski
    Michael R. Wasielewski
    Department of Chemistry and Institute for Sustainability and Energy at Northwestern, Northwestern University, Evanston, Illinois 60208-3113, United States
  • , and 
  • Erin T. Chernick*
    Erin T. Chernick
    Institute für Organische Chemie, University of Tübingen, Auf Der Morgenstelle 18, A-Bau, Tübingen 72076, Germany
    *Email: [email protected]
Cite this: J. Phys. Chem. A 2020, 124, 30, 6168–6176
Publication Date (Web):June 17, 2020
https://doi.org/10.1021/acs.jpca.0c03176
Copyright © 2020 American Chemical Society

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    Abstract

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    Switchable coupling between two qubits is important for quantum information science (QIS). As a proof of concept, a series of mesosubstituted porphyrins have been synthesized with a (2,2,6,6-tetramethylpiperidin-1-yl)oxyl stable free radical (SFR) appended and metalated with Cu(II), Ni(II), and Zn(II) in order to explore the interaction between the SFR doublet state and metalloporphyrin. The spin state of the porphyrin varies upon metal insertion, where Zn(II) is a diamagnetic metal, Cu(II) is paramagnetic, and Ni(II) can be switched from a diamagnetic square-planar structure to a paramagnetic octahedral state by complexation with a solvent (i.e., pyridine or tetrahydrofuran). Time-resolved electron paramagnetic resonance (EPR) measurements reveal that upon photoexcitation, the Zn(II) and free-base porphyrin species demonstrate different magnetic exchange regimes between the porphyrin triplet excited states and the SFR doublet state, with the Zn derivative populating a quartet state (i.e., moderate magnetic exchange), whereas the free-base derivative remains a triplet (i.e., weak magnetic exchange). Transient absorption measurements corroborate the TREPR results, demonstrating a 66% increase in the singlet excited-state decay rate due to enhanced intersystem crossing for the Zn(II) derivative in comparison to a modest 14% enhancement for the free-base porphyrin. These results enable the realization of a switchable qubit coupler, depending upon Zn metal insertion to the free-base porphyrin, which has potential QIS applications.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.0c03176.

    • Experimental details, including synthesis, NMR, mass spectrometry, steady-state absorption and fluorescence, TA spectra and kinetics, CW-EPR and TREPR spectra, and echo-detected transient nutation data (PDF)

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    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 6 publications.

    1. Koki Nishimura, Reiya Yabuki, Tomoyuki Hamachi, Nobuo Kimizuka, Kenichiro Tateishi, Tomohiro Uesaka, Nobuhiro Yanai. Dynamic Electron Polarization Lasting More Than 10 μs by Hybridizing Porphyrin and TEMPO with Flexible Linkers. The Journal of Physical Chemistry B 2023, 127 (5) , 1219-1228. https://doi.org/10.1021/acs.jpcb.2c07936
    2. Haochuan Mao, Ryan M. Young, Matthew D. Krzyaniak, Michael R. Wasielewski. Optical Initialization of Molecular Qubit Spin States Using Weak Exchange Coupling to Photogenerated Fullerene Triplet States. The Journal of Physical Chemistry B 2022, 126 (49) , 10519-10527. https://doi.org/10.1021/acs.jpcb.2c07096
    3. Maximilian Mayländer, Su Chen, Emmaline R. Lorenzo, Michael R. Wasielewski, Sabine Richert. Exploring Photogenerated Molecular Quartet States as Spin Qubits and Qudits. Journal of the American Chemical Society 2021, 143 (18) , 7050-7058. https://doi.org/10.1021/jacs.1c01620
    4. Theresia Quintes, Maximilian Mayländer, Sabine Richert. Properties and applications of photoexcited chromophore–radical systems. Nature Reviews Chemistry 2023, 7 (2) , 75-90. https://doi.org/10.1038/s41570-022-00453-y
    5. Knowledge Siyabonga Ndlovu, Makwena Justice Moloto, Kutloano Edward Sekhosana, Thabo Thokozani Innocent Nkambule, Muthumuni Managa. Porphyrins developed for photoinactivation of microbes in wastewater. Environmental Science and Pollution Research 2023, 30 (5) , 11210-11225. https://doi.org/10.1007/s11356-022-24644-8
    6. Yuri E. Kandrashkin, Marilena Di Valentin, Art van der Est. Reversible triplet energy hopping in photo-excited molecules: A two-site model for the spin polarization. The Journal of Chemical Physics 2020, 153 (9) https://doi.org/10.1063/5.0022164

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