Probing soft X-ray induced photoreduction of a model Mn-complex at cryogenic conditions
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 chemic...
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| Language: | English |
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International Union of Crystallography
2025-03-01
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| Series: | Journal of Synchrotron Radiation |
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| Online Access: | https://journals.iucr.org/paper?S1600577524012189 |
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| author | Kuntal Chatterjee Sang-Jun Lee Li-Cheng Kao Margaret D. Doyle Charles J. Titus Stephen R. Leone Junko Yano Vittal K. Yachandra Philippe Wernet Jan F. Kern |
| author_facet | Kuntal Chatterjee Sang-Jun Lee Li-Cheng Kao Margaret D. Doyle Charles J. Titus Stephen R. Leone Junko Yano Vittal K. Yachandra Philippe Wernet Jan F. Kern |
| author_sort | Kuntal Chatterjee |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-8728e7da1ccb4a138675ff74058da372 |
| institution | DOAJ |
| issn | 1600-5775 |
| language | English |
| publishDate | 2025-03-01 |
| publisher | International Union of Crystallography |
| record_format | Article |
| series | Journal of Synchrotron Radiation |
| spelling | doaj-art-8728e7da1ccb4a138675ff74058da3722025-08-20T02:46:08ZengInternational Union of CrystallographyJournal of Synchrotron Radiation1600-57752025-03-0132239940710.1107/S1600577524012189rv5186Probing soft X-ray induced photoreduction of a model Mn-complex at cryogenic conditionsKuntal Chatterjee0Sang-Jun Lee1Li-Cheng Kao2Margaret D. Doyle3Charles J. Titus4Stephen R. Leone5Junko Yano6Vittal K. Yachandra7Philippe Wernet8Jan F. Kern9Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USASLAC National Accelerator Laboratory, Menlo Park, CA 94025, USAMolecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USAMolecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USASLAC National Accelerator Laboratory, Menlo Park, CA 94025, USADepartment of Chemistry, University of California Berkeley, Berkeley, CA 94720, USAMolecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USAMolecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USADepartment of Physics and Astronomy, Uppsala University, 75120 Uppsala, SwedenMolecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USASoft 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.https://journals.iucr.org/paper?S1600577524012189l-edge spectroscopytransition metalsradiation damage |
| spellingShingle | Kuntal Chatterjee Sang-Jun Lee Li-Cheng Kao Margaret D. Doyle Charles J. Titus Stephen R. Leone Junko Yano Vittal K. Yachandra Philippe Wernet Jan F. Kern Probing soft X-ray induced photoreduction of a model Mn-complex at cryogenic conditions Journal of Synchrotron Radiation l-edge spectroscopy transition metals radiation damage |
| title | Probing soft X-ray induced photoreduction of a model Mn-complex at cryogenic conditions |
| title_full | Probing soft X-ray induced photoreduction of a model Mn-complex at cryogenic conditions |
| title_fullStr | Probing soft X-ray induced photoreduction of a model Mn-complex at cryogenic conditions |
| title_full_unstemmed | Probing soft X-ray induced photoreduction of a model Mn-complex at cryogenic conditions |
| title_short | Probing soft X-ray induced photoreduction of a model Mn-complex at cryogenic conditions |
| title_sort | probing soft x ray induced photoreduction of a model mn complex at cryogenic conditions |
| topic | l-edge spectroscopy transition metals radiation damage |
| url | https://journals.iucr.org/paper?S1600577524012189 |
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