在低温条件下探测软x射线诱导的模型mn复合物的光还原。

IF 2.5 3区 物理与天体物理
Journal of Synchrotron Radiation Pub Date : 2025-03-01 Epub Date: 2025-02-03 DOI:10.1107/S1600577524012189
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
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引用次数: 0

摘要

第一排跃迁元素各自l边的软x射线吸收光谱提供了金属中心氧化态和自旋态的重要信息。然而,辐射敏感样品的相关样品损伤实质上改变了氧化还原活性金属中心的电子和化学结构。在这里,我们用超导过渡边缘传感器探测器在八面体环境中测量了含有氧化还原活性MnIII金属中心的MnIII(acac)3模型配合物的软x射线光谱。为了减少主要由自由基和电子扩散引起的二次损伤,在固体样品的30k和80k下收集了光谱。从第一次扫描开始,我们检测到x射线诱导的样品损伤导致MnII强度变化的贡献。然而,在低温下,特别是在30 K时,我们没有观察到x射线连续扫描同一点的辐射损伤逐渐增加。在我们估计的90 kGy剂量下,我们发现62%的MnIII(acac)3在30 K时仍然完好无损。然而,在室温下,随着同一点扫描次数的增加,我们看到辐射损伤逐渐增加,这与其他研究中指出的二次自由基和电子扩散速率增加的可能性是一致的。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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 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.

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来源期刊
Journal of Synchrotron Radiation
Journal of Synchrotron Radiation INSTRUMENTS & INSTRUMENTATIONOPTICS&-OPTICS
CiteScore
5.60
自引率
12.00%
发文量
289
审稿时长
1 months
期刊介绍: Synchrotron radiation research is rapidly expanding with many new sources of radiation being created globally. Synchrotron radiation plays a leading role in pure science and in emerging technologies. The Journal of Synchrotron Radiation provides comprehensive coverage of the entire field of synchrotron radiation and free-electron laser research including instrumentation, theory, computing and scientific applications in areas such as biology, nanoscience and materials science. Rapid publication ensures an up-to-date information resource for scientists and engineers in the field.
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