Heterotrimetallic Precursor with 2:2:1 Metal Ratio Requires at Least a Pentanuclear Molecular Assembly,Journal of the American Chemical Society

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Heterotrimetallic Precursor with 2:2:1 Metal Ratio Requires at Least a Pentanuclear Molecular Assembly
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-06-23 , DOI: 10.1021/jacs.0c05139
Haixiang Han _{1,

2} , Jesse C Carozza ₁ , Zheng Zhou ₁ , Yuxuan Zhang ₁ , Zheng Wei ₁ , Artem M Abakumov ₃ , Alexander S Filatov ₄ , Yu-Sheng Chen ₅ , Daniel J SantaLucia ₆ , John F Berry ₆ , Evgeny V Dikarev ₁

Affiliation

This work represents an important step towards the quest to make heteromultimetallic molecules featuring specific metal types and complicated metal ratios. The rational design, synthesis, and characterization of a complex heterotrimetallic single-source molecular precursor for the next generation sodium-ion battery cathode material, Na2Mn2FeO6, is described. A unique pentametallic platform [MnII(ptac)3-Na-MnIII(acac)3-Na-MnII(ptac)3] (1) was derived from the known polymeric structure of [NaMnII(acac)3]∞, through a series of elaborate design procedures, such as mixed-ligand, unsymmetric ligand, and mixed-valent approaches. Importantly, the application of those techniques results in a molecule with distinctively different transition metal positions in terms of ligand environment and oxidation states. An isovalent substitution of FeIII for the central MnIII ion forms the target heterotrimetallic precursor [MnII(ptac)3-Na-FeIII(acac)3-Na-MnII(ptac)3] (3) with an appropriate metal ratio of Na:Mn:Fe = 2:2:1. The arrangement of metal ions and ligands in this pentametallic assembly was confirmed by single crystal X-ray investigation. The unambiguous assignment of the positions and oxidation states of the Periodic Table neighbors Fe and Mn in 3 has been achieved by a combination of investigative techniques that include synchrotron resonant diffraction, X-ray multiwavelength anomalous diffraction, X-ray fluorescence spectroscopy, Mössbauer spectroscopy, and gas-phase DART mass spectrometry. The heterotrimetallic single-source precursor 3 was shown to exhibit a clean decomposition pattern yielding the phase-pure P2-NaxMn2FeO6 quaternary oxide with high uniformity of metal ion distribution as confirmed by electron microscopy.

中文翻译：

金属比为 2:2:1 的异三金属前驱体至少需要五核分子组装

这项工作代表了寻求制造具有特定金属类型和复杂金属比例的异质多金属分子的重要一步。描述了用于下一代钠离子电池正极材料 Na2Mn2FeO6 的复杂异质三金属单源分子前体的合理设计、合成和表征。一个独特的五金属平台 [MnII(ptac)3-Na-MnIII(acac)3-Na-MnII(ptac)3] (1) 源自 [NaMnII(acac)3]∞ 的已知聚合结构，通过一系列复杂的设计程序，例如混合配体、不对称配体和混合价方法。重要的是，这些技术的应用导致分子在配体环境和氧化态方面具有明显不同的过渡金属位置。FeIII 对中心 MnIII 离子的等价取代形成目标异三金属前体 [MnII(ptac)3-Na-FeIII(acac)3-Na-MnII(ptac)3] (3)，具有适当的 Na:Mn 金属比:Fe = 2:2:1。通过单晶 X 射线研究证实了该五金属组件中金属离子和配体的排列。通过结合研究技术，包括同步辐射共振衍射、X 射线多波长异常衍射、X 射线荧光光谱、穆斯堡尔光谱、和气相 DART 质谱。

更新日期：2020-06-23

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