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

Sreejith Shankar, Morten Peters, Kim Steinborn, Bahne Krahwinkel, Frank D. Sönnichsen, Dirk Grote, Wolfram Sander, Thomas Lohmiller, Olaf Rüdiger and Rainer Herges ()
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Sreejith Shankar: University of Kiel
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
Olaf Rüdiger: Max-Planck-Institute for Chemical Energy Conversion
Rainer Herges: University of Kiel

Nature Communications, 2018, vol. 9, issue 1, 1-12

Abstract: 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.

Date: 2018
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DOI: 10.1038/s41467-018-07023-1

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