Synthesis of an Oxo-Bridged Fe(III) Porphyrin(2.1.2.1) Dimer and Its Enhanced Electrocatalytic Oxygen Evolution
A Fe(III) porphyrin(2.1.2.1) oxo-bridged dimer complex was synthesized using porphyrin(2.1.2.1) as a bent ligand. The resulting complex adopts an oxo-bridged and cross-stacked molecular structure. DFT calculations reveal antiferromagnetic coupling between the two iron centers, characterized by an exchange coupling constant of <i>J</i> = -129.5 cm<sup>-1</sup>. TDDFT simulations reproduce the key features of the experimental UV-vis spectrum, indicating that the brightest transitions correspond to a predominantly LMCT (π → d) character. The electrocatalytic OER study and DFT-based mechanistic analysis demonstrate that the bridging oxo ligand plays an important role in enhancing catalytic activity, with a lower overpotential for the rate-determining step.
Authors
- Yingjin Wei (ORCID: https://orcid.org/0000-0002-9375-9272)
- Hiroko Yamada (ORCID: https://orcid.org/0000-0002-2138-5902)
- Nikolay V. Tkachenko (ORCID: https://orcid.org/0000-0002-7296-4293)
- Yuanbo Zhou (ORCID: https://orcid.org/0000-0003-0351-5790)
- Shihao Liu (ORCID: https://orcid.org/0000-0002-0645-5319)
- Zhongti Sun (ORCID: https://orcid.org/0000-0002-4754-6583)
- Zuyu Zhang
- Songlin Xue (ORCID: https://orcid.org/0000-0002-6197-1885)
- Yue Wang (ORCID: https://orcid.org/0000-0003-2816-3234)
- Tao Ye (ORCID: https://orcid.org/0000-0003-4768-1811)
- Xiaohui Zhao (ORCID: https://orcid.org/0000-0002-2060-6961)
- Ru Feng (ORCID: https://orcid.org/0009-0009-7080-1712)
- Fengxian Qiu (ORCID: https://orcid.org/0000-0002-1822-1181)
Institutions
- Jiangsu University (CN)
- Kyoto University (JP)
- Soochow University (CN)
- City University (BD)
- Ministry of Education (BD)
- Kyoto University Institute for Chemical Research
- Suzhou City University
- University of Oklahoma (US)
- Anhui University of Technology (CN)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2025-11-06
- DOI
- https://doi.org/10.1021/acs.inorgchem.5c04140
- Primary Topic
- Porphyrin and Phthalocyanine Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.00