南京师范大学陈旭东团队报道了具有二十面体[Fe@Fe₁₂]¹⁶⁺核心的铁簇合物的合成与表征。相关研究成果发表在2023年12月22日出版的《国家科学评论》。

铁金属簇在各种关键的生物和材料系统中至关重要，包括金属酶、催化剂和磁性存储设备。然而，由于难以通过铁-铁直接键合来稳定物种，从未合成高核铁簇。

该文中，研究人员合成、结晶并表征了(Tp*)₄W₄S₁₂(Fe@Fe₁₂) 簇（Tp*=三（3,5-二甲基-1-吡唑基）硼酸酯（1）），其具有罕见的三叉核二十面体[Fe@Fe₁₂]在间隙铁（Fe_i）和外围铁（Fe_p）之间具有直接多中心铁-铁键合的簇芯，以及Fe_p··Fe_p铁磁耦合。

量子化学研究表明，团簇的稳定性源于 [Fe@Fe₁₂]¹⁶⁺核心，通过其与外围三齿[（Tp*）WS₃]^4-配体的键合相互作用来辅助，所述配体同时具有S→Fe供给和自旋极化的Fe-Wσ键。理论上预测团簇的基态电子自旋为S＝32/2。该化合物中低氧化态（OS～+1.23）铁的存在可能在磁存储、自旋电子学、氧化还原化学和团簇催化等领域有着有趣的应用。

附：英文原文

Title: Synthesis and Characterization of Iron Clusters with an Icosahedral [Fe@Fe12]16+ Core

Author: Xu, Gan, Cui, Yun-Shu, Jiang, Xue-Lian, Xu, Cong-Qiao, Li, Jun, Chen, Xu-Dong

Issue&Volume: 2023-12-22

Abstract: Iron-metal clusters are crucial in a variety of critical biological and material systems, including metalloenzymes, catalysts, and magnetic storage devices. However, 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*)4W4S12(Fe@Fe12) cluster (Tp* = tris(3,5-dimethyl-1-pyrazolyl)borate(1)), which features a rare trideca-nuclear, icosahedral [Fe@Fe12] cluster core with direct multicenter iron-iron bonding between the interstitial iron (Fei) and peripheral irons (Fep), as well as Fep···Fep ferromagnetic coupling. Quantum chemistry studies reveal that the stability of the cluster arises from the 18-electron shell-closing of the [Fe@Fe12]16+ core, assisted by its bonding interactions with the peripheral tridentate [(Tp*)WS3]4 ligands which possess both the 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.

DOI: 10.1093/nsr/nwad327

Source: https://academic.oup.com/nsr/advance-article/doi/10.1093/nsr/nwad327/7492299searchresult=1