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Light-controlled switching of the spin state of iron(III)

Author

Listed:
  • Sreejith Shankar

    (University of Kiel
    Chemical Sciences and Technology Division, CSIR – National Institute for Interdisciplinary Sciences and Technology (CSIR – NIIST))

  • Morten Peters

    (University of Kiel)

  • Kim Steinborn

    (University of Kiel)

  • Bahne Krahwinkel

    (University of Kiel)

  • Frank D. Sönnichsen

    (University of Kiel)

  • Dirk Grote

    (Organic Chemistry II)

  • Wolfram Sander

    (Organic Chemistry II)

  • Thomas Lohmiller

    (Max-Planck-Institute for Chemical Energy Conversion
    Institute for Nanospectroscopy, Helmholtz-Zentrum Berlin für Materialien und Energie, Kekuléstraße 5)

  • Olaf Rüdiger

    (Max-Planck-Institute for Chemical Energy Conversion)

  • Rainer Herges

    (University of Kiel)

Abstract

Controlled switching of the spin state of transition metal ions, particularly of FeII and FeIII, is a prerequisite to achieve selectivity, efficiency, and catalysis in a number of metalloenzymes. Here we report on an iron(III) porphyrin with a photochromic axial ligand which, upon irradiation with two different wavelengths reversibly switches its spin state between low-spin (S = 1/2) and high-spin (S = 5/2) in solution (DMSO-acetone, 2:598). The switching efficiency is 76% at room temperature. The system is neither oxygen nor water sensitive, and no fatigue was observed after more than 1000 switching cycles. Concomitant with the spin-flip is a change in redox potential by ~60 mV. Besides serving as a simple model for the first step of the cytochrome P450 catalytic cycle, the spin switch can be used to switch the spin-lattice relaxation time T1 of the water protons by a factor of 15.

Suggested Citation

  • Sreejith Shankar & Morten Peters & Kim Steinborn & Bahne Krahwinkel & Frank D. Sönnichsen & Dirk Grote & Wolfram Sander & Thomas Lohmiller & Olaf Rüdiger & Rainer Herges, 2018. "Light-controlled switching of the spin state of iron(III)," Nature Communications, Nature, vol. 9(1), pages 1-12, December.
    • Handle: RePEc:nat:natcom:v:9:y:2018:i:1:d:10.1038_s41467-018-07023-1
    DOI: 10.1038/s41467-018-07023-1
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