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

IF 16.3 1区综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES

National Science Review Pub Date : 2023-12-23 DOI:10.1093/nsr/nwad327

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

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引用次数: 0

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.

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具有二十面体 [Fe@Fe12]16+ 核心的铁簇的合成与表征

铁-金属团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，由于稳定具有直接铁-铁键的物种极其困难，因此一直没有合成高核铁簇。在这项工作中，我们合成、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-)），它具有罕见的十核二十面体[Fe@Fe12]簇核，间隙铁（Fei）和外围铁（Fep）之间存在直接的多中心铁-铁键，以及 Fep---Fep 铁磁耦合。量子化学研究表明，簇合物的稳定性来自于[Fe@Fe12]16+ 核心的 18 电子闭壳，以及它与外围三叉[(Tp*)WS3]4-配体的成键相互作用。根据理论预测，该簇的基态电子自旋为 S = 32/2。这种化合物中存在的低氧化态（OS ∼ +1.23）铁可能会在磁存储、自旋电子学、氧化还原化学和簇催化中找到有趣的应用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

National Science Review MULTIDISCIPLINARY SCIENCES-

CiteScore

24.10

自引率

1.90%

发文量

249

审稿时长

13 weeks

期刊介绍： National Science Review (NSR; ISSN abbreviation: Natl. Sci. Rev.) is an English-language peer-reviewed multidisciplinary open-access scientific journal published by Oxford University Press under the auspices of the Chinese Academy of Sciences.According to Journal Citation Reports, its 2021 impact factor was 23.178. National Science Review publishes both review articles and perspectives as well as original research in the form of brief communications and research articles.