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Peer-reviewedCC BY 4.0Inorganic Chemistry

Impact of the Metal–Ligand Bonding Nature on Electronic States of {Fe(NO)2}9/10–{Fe(NO)2}9/10 RREs Unraveled by the Combined X‑ray Spectroscopic Analyses: Relevance to DNIC-Mediated Translational Functionality

  • Sen-Hung Hsieh1
  • Jia-Yu Lin2
  • Feng-Tian Chang1
  • Chi-Yen Tung1
  • Nozomu Hiraoka3,4
  • Shu-Chih Haw3
  • Fu-Te Tsai1,5
  • I-Jui Hsu2
  • Wen-Feng Liaw1
5 affiliations
  1. 1Department of Chemistry, National Tsing Hua University, Hsinchu 300044, Taiwan
  2. 2Research and Development Center for Smart Textile Technology, Department of Molecular Science and Engineering, National Taipei University of Technology, Taipei 106344, Taiwan
  3. 3National Synchrotron Radiation Research Center (NSRRC), Hsinchu 300092, Taiwan
  4. 4Japan Synchrotron Radiation Research Institute (JASRI/SPring-8), Hyogo 6795198, Japan
  5. 5Department of Applied Chemistry, National Chiayi University, Chiayi 600355, Taiwan
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Abstract

Probed by the combined X-ray spectroscopic techniques (N K-edge/Fe L-edge XAS, Fe K-edge HERFD–XANES, Kβ1,3 mainline, VtC Kβ2,5 XES) and DFT computation, the qualitative/quantitative assignment of Fe/NO oxidation states in dinuclear dinitrosyl iron complexes (DNICs) suggests that the balance between NO– → Fe π-donating and Fe → •NO π-backbonding interactions in the [Fe­(NO)2] unit(s) is modulated by the ionicity-covalency competition within the Fe–ER(2) bonds for a series of [ER(2)]−-bridged {Fe­(NO)2}9/10–{Fe­(NO)2}9/10 RREs (E = S, N, O). With the delicately ligand-controlled NO–/•NO equilibrium in the [Fe­(NO)2] unit, the biomimetic activity governed by {Fe­(NO)2}9/{Fe­(NO)2}10 DNICs echoes their electronic/spectroscopic features, which not only uncovers molecular identity in complex environments but also decodes the reported H2S/NO communication, degradation/repair of [Fe–S] clusters, and translational functionality for NO-to-[N2O2]2–-to-N2O and NO-to-HNO/NO– transformations.

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Cite

BibTeXRIS
BibTeX
@article{hsieh2026impact,
  title = {{Impact of the Metal–Ligand Bonding Nature on Electronic States of Fe(NO)29/10–Fe(NO)29/10 RREs Unraveled by the Combined X‑ray Spectroscopic Analyses: Relevance to DNIC-Mediated Translational Functionality}},
  author = {Sen-Hung Hsieh and Jia-Yu Lin and Feng-Tian Chang and Chi-Yen Tung and Nozomu Hiraoka and Shu-Chih Haw and Fu-Te Tsai and I-Jui Hsu and Wen-Feng Liaw},
  journal = {Inorganic Chemistry},
  year = {2026},
  month = oct,
  doi = {10.1021/acs.inorgchem.6c03317},
  url = {https://doi.org/10.1021/acs.inorgchem.6c03317},
  note = {CC BY 4.0},
}
RIS
TY  - JOUR
TI  - Impact of the Metal–Ligand Bonding Nature on Electronic States of {Fe(NO)2}9/10–{Fe(NO)2}9/10 RREs Unraveled by the Combined X‑ray Spectroscopic Analyses: Relevance to DNIC-Mediated Translational Functionality
AU  - Sen-Hung Hsieh
AU  - Jia-Yu Lin
AU  - Feng-Tian Chang
AU  - Chi-Yen Tung
AU  - Nozomu Hiraoka
AU  - Shu-Chih Haw
AU  - Fu-Te Tsai
AU  - I-Jui Hsu
AU  - Wen-Feng Liaw
PY  - 2026
DA  - 2026/10/19
JO  - Inorganic Chemistry
DO  - 10.1021/acs.inorgchem.6c03317
UR  - https://doi.org/10.1021/acs.inorgchem.6c03317
AB  - Probed by the combined X-ray spectroscopic techniques (N K-edge/Fe L-edge XAS, Fe K-edge HERFD–XANES, Kβ1,3 mainline, VtC Kβ2,5 XES) and DFT computation, the qualitative/quantitative assignment of Fe/NO oxidation states in dinuclear dinitrosyl iron complexes (DNICs) suggests that the balance between NO– → Fe π-donating and Fe → •NO π-backbonding interactions in the [Fe­(NO)2] unit(s) is modulated by the ionicity-covalency competition within the Fe–ER(2) bonds for a series of [ER(2)]−-bridged {Fe­(NO)2}9/10–{Fe­(NO)2}9/10 RREs (E = S, N, O). With the delicately ligand-controlled NO–/•NO equilibrium in the [Fe­(NO)2] unit, the biomimetic activity governed by {Fe­(NO)2}9/{Fe­(NO)2}10 DNICs echoes their electronic/spectroscopic features, which not only uncovers molecular identity in complex environments but also decodes the reported H2S/NO communication, degradation/repair of [Fe–S] clusters, and translational functionality for NO-to-[N2O2]2–-to-N2O and NO-to-HNO/NO– transformations.
SN  - 0020-1669
SN  - 1520-510X
ER  -