Citation: Chunhui Wang, Xinyi Ji, Puyong He, Chaoyue Fan, Yuan Gao, Zhe Han, Jie Qiu. β-Anderson-type antiferromagnetic iron oxo clusters for catalysis in Aldehyde Cyanosilylation[J]. Chinese Chemical Letters, ;2026, 37(11): 111755. doi: 10.1016/j.cclet.2025.111755 shu

β-Anderson-type antiferromagnetic iron oxo clusters for catalysis in Aldehyde Cyanosilylation

School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an 710049, China

Received Date: 18 July 2025
Revised Date: 15 August 2025
Accepted Date: 25 August 2025
Available Online: 26 August 2025

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The rational synthesis of structurally novel metal oxo clusters remains pivotal for advancing materials chemistry and catalysis. Herein, we report four unprecedented iron oxo clusters, featuring groundbreaking structural motifs and exceptional catalytic activity. The heptanuclear clusters [Fe₇O₂(SO₄)₂(CH₃O)₁₀Cl₆]·3(C₅H₆N)·5(H₂O) (abbreviated as Fe₇(SO₄)₂) and [Fe₇O₂(SeO₄)₂(CH₃O)₁₀Cl₆]·3(C₅H₆N)·6(H₂O) (abbreviated as Fe₇(SeO₄)₂) represent not only the first iron clusters but also rare homometallic clusters that exhibit β-Anderson-type structures. Strikingly, substituting pyridine with 3-methylpyridine in solvothermal synthesis reactions results in the formation of two tetranuclear iron clusters, [Fe₄O(SO₄)₂(CH₃O)₅Cl₄]·3(C₆H₈N) (abbreviated as Fe₄(SO₄)₂) and [Fe₄O(SeO₄)₂(CH₃O)₅Cl₄]·3(C₆H₈N)·(CH₃OH)·9(H₂O) (abbreviated as Fe₄(SeO₄)₂), which exhibit unusual structures with half β-Anderson configuration. These results demonstrate the critical role of organic amines in directing the formation and nuclearity of iron oxo clusters. All clusters exhibit similar antiferromagnetic behaviors and ultraviolet-visible (UV-vis) adsorption spectra arising from the ligand-to-metal charge transfer. Most importantly, they show excellent Lewis acid catalytic activities and stabilities in the cyanosilylation reaction of aldehydes, highlighting the promising applications of iron oxo clusters as a sustainable, high-performance catalysis. This work establishes an organic amine-guided strategy for designing polynuclear iron architectures with combined structural novelty and catalytic prowess.
- Metal-oxo cluster,
- β-Anderson-type structures,
- Organic amines,
- Magnetism,
- Cyanosilylation of aldehydes
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