红外电子顺磁共振直接测定三态有机双硫醚中5422 cm-1的巨零场分裂

IF 14.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2024-12-16 DOI:10.1021/jacs.4c14795

Tarek Al Said, Davide Spinnato, Karsten Holldack, Frank Neese, Josep Cornella, Alexander Schnegg

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引用次数: 0

摘要

稳定的单配位有机铋烯直到最近才被分离出来，并对其化学和电子结构进行了分析。对 tBu-MSFluind-Bi(I) (2) 的量子化学计算预示了一种不寻常的电子结构，它以三重基态和惊人的零场分裂（ZFS）> 4500 cm-1 为主导。然而，由于现有磁性表征技术的限制，这些预测的实验证据仍然难以捉摸。在这里，我们利用磁光红外光谱直接检测三重电子顺磁共振，确定了 2 的轴向 ZFS 为 D = 5422 cm-1。这是迄今为止通过实验测得的最大 ZFS。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Direct Determination of a Giant Zero-Field Splitting of 5422 cm–1 in a Triplet Organobismuthinidene by Infrared Electron Paramagnetic Resonance

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Direct Determination of a Giant Zero-Field Splitting of 5422 cm–1 in a Triplet Organobismuthinidene by Infrared Electron Paramagnetic Resonance

Stable monocoordinated organobismuthinidenes were only recently isolated and analyzed toward their chemical and electronic structure. Quantum chemical calculations on ^tBu-M^SFluind-Bi(I) (2) predicted an unusual electronic structure dominated by a triplet ground state and a spectacular zero-field splitting (ZFS) > 4500 cm^–1. However, experimental evidence for these predictions remained elusive due to limitations in the available magnetic characterization techniques. Herein, we determine an axial ZFS of D = 5422 cm^–1 for 2, by direct detection of triplet electron paramagnetic resonance using magneto-optical infrared spectroscopy. To date, this represents the largest ZFS experimentally measured.

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来源期刊

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.