铕(II)和锶(II)的膦酰基和胂酰基三癸基三明治配合物

IF 8.5 Q1 CHEMISTRY, MULTIDISCIPLINARY JACS Au Pub Date : 2024-06-06 DOI:10.1021/jacsau.4c00300
Noah Schwarz, Julia Feye, Vanitha R. Naina, Ralf Köppe, Sebastian Gillhuber, Xiaofei Sun and Peter W. Roesky*, 
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摘要

为了研究杂原子对二价 Eu 和 Sr 复合物光物理性质的影响,合成了膦酰基和胂酰基化合物[{(Dtp)(thf)M}2{μ-η8:M = EuII 和 SrII;Dtp = 3,4-二甲基-2,5-双(叔丁基)膦酰基)和 [{(Dtas)(thf)M}2{μ-η8:η8-C8H8}] (M = EuII 和 SrII;Dtas = 3,4-二甲基-2,5-双(叔丁基)胂酰基)。二价铕与 P 和 As 杂环配体的有机金属化合物以前从未描述过。这些化合物是通过膦酰或胂酰钾、K2C8H8 和 EuI2(thf)2 或 SrI2 的消盐反应制备的。与结构相似的环戊二烯参考络合物一起研究了它们的光物理特性。重要的是,杂原子对配合物的光致发光发射、激发和量子产率的影响很大。为了合理解释配体的影响,我们进行了密度泛函理论计算。
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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Phospholyl and Arsolyl Triple-Decker Sandwich Complexes of Europium(II) and Strontium(II)

To study the influence of heteroatoms on the photophysical properties of divalent Eu and Sr complexes, the synthesis of the phospholyl and arsolyl compounds [{(Dtp)(thf)M}2{μ-η88-C8H8}] (M = EuII and SrII; Dtp = 3,4-dimethyl-2,5-bis(tert-butyl)phospholyl) and [{(Dtas)(thf)M}2{μ-η88-C8H8}] (M = EuII and SrII; Dtas = 3,4-dimethyl-2,5-bis(tert-butyl)arsolyl) is reported. Organometallic compounds of divalent europium with P and As heterocyclic ligands have not been described previously. They were prepared by salt elimination reactions from potassium phospholyl or arsolyl, K2C8H8, and EuI2(thf)2 or SrI2. Photophysical properties were investigated alongside a reference cyclopentadienyl complex with a comparable structure. Critically, the influence of the heteroatom on the photoluminescence emission and excitation and quantum yields of the complexes is significant. Density functional theory calculations were performed to rationalize the ligand influences.

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