A high-nuclearity vanadium(III,IV) cyclic coordination cluster with small ground spin state
Abstract Low-valent vanadium(III) with d2 electronic configuration, which can generate significant magnetic anisotropy, is highly desirable for the construction of high-performance molecule-based magnetic materials. Such lightweight and flexible magnetic materials cannot be realized by conventional inorganic or alloy-based permanent magnets. However, owing to the facile oxidation of vanadium(III), the synthesis of stable complexes containing highly reduced V(III) or mixed low-valent V(III,IV) centers remains extremely challenging. To date, only a limited number of V(III) or V(III,IV)-based coordination complexes or clusters have been isolated, most of which possess a nuclearity lower than eighteen. Herein, we report the self-assembly of a giant V(III,IV) cluster, namely {VIII20VIV2O8(OH)8(CH3COO)24(CH3CH2O)20}·5CH3CH2OH (V22), from a trinuclear vanadium precursor. The resulting large V22 cyclic coordination cluster exhibits an unusual small triplet ground spin state, which arises from antiferromagnetic exchange interactions. Moreover, this cluster system is detectable by electron paramagnetic resonance (EPR) spectroscopy and displays prominent quantum characteristics.
Authors
- Petr Neugebauer (ORCID: https://orcid.org/0000-0001-7095-6401)
- Joris van Slageren (ORCID: https://orcid.org/0000-0002-0855-8960)
- Anatoly R. Melnikov (ORCID: https://orcid.org/0000-0002-0458-5742)
- Ismael F. Díaz‐Ortega (ORCID: https://orcid.org/0000-0002-6150-4611)
- Qian‐Cheng Luo (ORCID: https://orcid.org/0000-0002-9693-8524)
- Yingqiu Dai (ORCID: https://orcid.org/0009-0002-7554-9340)
- Sergey L. Veber (ORCID: https://orcid.org/0000-0002-5445-3713)
- Zhongwen Ouyang
- Weipeng Chen (ORCID: https://orcid.org/0000-0001-6396-9300)
- Ji-Hu Su
- Yuan-Qi Zhai
- Zhenxing Wang
- Xing Rong
- Xia-Li Ding
- Yan-Zhen Zheng
- Hiroyuki Nojiri
Institutions
- University of Stuttgart (DE)
- University of Science and Technology of China (CN)
- Central European Institute of Technology (CZ)
- Shaanxi University of Technology (CN)
- Tohoku University (JP)
- Laboratoire National des Champs Magnétiques Intenses (FR)
- Technology Holding (United States) (US)
- High Magnetic Field Laboratory (CN)
- Shaanxi Science and Technology Department (CN)
- National High Magnetic Field Laboratory (US)
- International Tomography Center (RU)
- Institute for Materials Research, Tohoku University (JP)
- University of Almería (ES)
- Brno University of Technology (CZ)
- Xi'an Jiaotong University (CN)
Publication Details
- Journal
- Polyoxometalates
- Published
- 2026-10-28
- DOI
- https://doi.org/10.26599/pom.2026.9140171
- Primary Topic
- Magnetism in coordination complexes
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Deutsche Forschungsgemeinschaft
- National Natural Science Foundation of China
- Xi’an Jiaotong University
- Bijzonder Onderzoeksfonds UGent
- Fundamental Research Funds for the Central Universities
- Division of Materials Research