Synthesis and characterization of iron clusters with an icosahedral [Fe@Fe12]16+ Core

Xu，Gan1; Cui，Yun Shu2; Jiang，Xue Lian2; Xu，Cong Qiao2; Li，Jun2,3; Chen，Xu Dong1,4

2024-04-01

10.1093/nsr/nwad327

National Science Review   影响因子和分区

2095-5138

2053-714X

Iron-metal clusters are crucial in a variety of critical biological and material systems, including metalloenzymes, catalysts, and magnetic storage devices. However, a synthetic high-nuclear iron cluster has been absent due to the extreme difficulty in stabilizing species with direct iron−iron bonding. In this work, we have synthesized, crystallized, and characterized a (Tp*)WS(Fe@Fe) cluster (Tp* = tris(3,5-dimethyl-1-pyrazolyl)borate(1−)), which features a rare trideca-nuclear, icosahedral [Fe@Fe] cluster core with direct multicenter iron−iron bonding between the interstitial iron (Fe) and peripheral irons (Fe), as well as Fe···Fe ferromagnetic coupling. Quantum chemistry studies reveal that the stability of the cluster arises from the 18-electron shell-closing of the [Fe@Fe] core, assisted by its bonding interactions with the peripheral tridentate [(Tp*)WS] ligands which possess both S→Fe donation and spin-polarized Fe−W σ bonds. The ground-state electron spin is theoretically predicted to be S = 32/2 for the cluster. The existence of low oxidation-state (OS ∼ +1.23) iron in this compound may find interesting applications in magnetic storage, spintronics, redox chemistry, and cluster catalysis.

Fe13 cluster high spin complex iron-sulfur cluster iron−iron bond low-valence iron

SCI ; EI

英语

通讯

2-s2.0-85184842635

Scopus

1.Jiangsu Collaborative Innovation Center of Biomedical Functional Materials,Jiangsu Key Laboratory of New Power Batteries,School of Chemistry and Materials Science,Nanjing Normal University,Nanjing,210023,China
2.Department of Chemistry,Guangdong Provincial Key Laboratory of Catalytic Chemistry,Southern University of Science and Technology,Shenzhen,518055,China
3.Department of Chemistry,Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education,Tsinghua University,Beijing,100084,China
4.State Key Laboratory of Coordination Chemistry,Nanjing University,Nanjing,210093,China

Xu，Gan,Cui，Yun Shu,Jiang，Xue Lian,et al. Synthesis and characterization of iron clusters with an icosahedral [Fe@Fe12]16+ Core[J]. National Science Review,2024,11(4).

Xu，Gan,Cui，Yun Shu,Jiang，Xue Lian,Xu，Cong Qiao,Li，Jun,&Chen，Xu Dong.(2024).Synthesis and characterization of iron clusters with an icosahedral [Fe@Fe12]16+ Core.National Science Review,11(4).

Xu，Gan,et al."Synthesis and characterization of iron clusters with an icosahedral [Fe@Fe12]16+ Core".National Science Review 11.4(2024).