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Probing soft X-ray induced photoreduction of a model Mn-complex at cryogenic conditions
Lawrence Berkeley Natl Lab, Mol Biophys & Integrated Bioimaging Div, Berkeley, CA 94720 USA.;Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA.;Lawrence Berkeley Natl Lab, Div Chem Sci, Berkeley, CA 94720 USA..
SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA..
Lawrence Berkeley Natl Lab, Mol Biophys & Integrated Bioimaging Div, Berkeley, CA 94720 USA..
Lawrence Berkeley Natl Lab, Mol Biophys & Integrated Bioimaging Div, Berkeley, CA 94720 USA..ORCID iD: 0000-0002-7289-3544
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2025 (English)In: Journal of Synchrotron Radiation, ISSN 0909-0495, E-ISSN 1600-5775, Vol. 32, p. 399-407Article in journal (Refereed) Published
Abstract [en]

Soft X-ray absorption spectroscopy of first row transition elements at their respective L-edges provides important information about the oxidation and spin states of the metal centers. However, the associated sample damage in radiation-sensitive samples substantially alters the electronic and chemical structures of redox-active metal centers. Here, we measure the soft X-ray spectrum of the model MnIII(acac)3 complex containing a redox-active MnIII metal center in an octahedral environment with a superconducting transition-edge sensor detector. To reduce the secondary damage resulting primarily from the diffusion of radicals and electrons, the spectra are collected at 30 K and 80 K on solid samples. Starting from the first scan, we detect the contribution of X-ray induced sample damage leading to a change in the MnII intensity. However, at low temperatures, particularly at 30 K, we do not observe a gradual increase in the radiation damage with successive scans with the X-ray beam at the same spot. At our estimated dose of 90 kGy, we find 62% of MnIII(acac)3 is still intact at 30 K. However, at room temperature, we see a gradual increase in radiation damage with increasing numbers of scans at the same spot, which is consistent with the possibility of increased diffusion rates of secondary radicals and electrons as noted in other studies.

Place, publisher, year, edition, pages
International Union Of Crystallography, 2025. Vol. 32, p. 399-407
Keywords [en]
L-edge spectroscopy, transition metals, radiation damage
National Category
Materials Chemistry Condensed Matter Physics Subatomic Physics
Identifiers
URN: urn:nbn:se:uu:diva-555011DOI: 10.1107/S1600577524012189ISI: 001441691900015PubMedID: 39899410Scopus ID: 2-s2.0-105001218288OAI: oai:DiVA.org:uu-555011DiVA, id: diva2:1953863
Funder
NIH (National Institutes of Health)German Research Foundation (DFG), 457346698Available from: 2025-04-23 Created: 2025-04-23 Last updated: 2025-04-23Bibliographically approved

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