Please use this identifier to cite or link to this item: http://localhost:8080/xmlui/handle/123456789/3389
Title: Light-controlled switching of the spin state of iron(III)
Authors: Sreejith, S
Peters, M
Steinborn, K
Krahwinkel, B
Sonnichsen, F D
Grote, D
Sander, W
Lohmiller, T
Rudiger, O
Herges, R
Issue Date: 12-Nov-2018
Publisher: Nature
Citation: Nature Communications; 9(1):4750
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.
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