Photon-Modulated Bond Covalency of [Sm(II)(η⁹-C₉H₉)₂].

IF 14.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Journal of the American Chemical Society Pub Date : 2024-07-31 Epub Date: 2024-07-05 DOI:10.1021/jacs.3c13934

T Vitova, H Ramanantoanina, B Schacherl, L Münzfeld, A Hauser, R S K Ekanayake, C Y Reitz, T Prüßmann, T S Neill, J Göttlicher, R Steininger, V A Saveleva, M W Haverkort, P W Roesky

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Abstract

Lanthanides are widely assumed not to form covalent bonds due to the localized nature of their 4f valence electrons. This work demonstrates that the ionic bond of Sm(II) with cyclononatetraenyl (η⁹-C₉H₉^-) in [Sm(η⁹-C₉H₉)₂] can be modulated and becomes more covalent by photon-induced transfer of Sm 4f electrons to Sm 5d orbitals. This photon-induced change in bonding properties facilitates a subsequent reconfiguration of [Sm(η₉-C₉H₉)₂]. As a result, Sm-C bond length contraction is detected and the local Sm coordination environment exhibits more extensive disorder. Both Sm 4f and 5d electrons have increased participation in covalent Sm-ligand interactions. The Sm L₃-edge valence band resonant inelastic X-ray scattering (VB-RIXS), high-resolution X-ray absorption near-edge structure (HR-XANES), and quantum chemical computations showcase a spectroscopic methodology for in-depth studies of bond covalency of lanthanide atoms.

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光子调节的[Sm(II)(η9-C9H9)2]键共价。

人们普遍认为镧系元素不会形成共价键，这是因为它们的 4f 价电子具有局部性。这项研究表明，通过光子诱导 Sm 4f 电子转移到 Sm 5d 轨道，[Sm(η9-C9H9)2] 中 Sm(II) 与环四烯基 (η9-C9H9-)的离子键可以被调节，并变得更具共价性。这种光子诱导的成键性质变化促进了[Sm(η9-C9H9)2]的后续重构。结果，检测到 Sm-C 键长度收缩，局部 Sm 配位环境呈现出更广泛的无序性。Sm 4f 和 5d 电子在 Sm 配体共价相互作用中的参与度都有所提高。Sm L3 边价带共振非弹性 X 射线散射（VB-RIXS）、高分辨率 X 射线吸收近边结构（HR-XANES）和量子化学计算展示了深入研究镧系元素共价键的光谱方法。

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

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.