稳定的三(二硫环戊烯)三烷基铝

IF 15.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Phuong M. Tran, Yuzhong Wang, Boris Dzikovski, Mitchell E. Lahm, Yaoming Xie, Pingrong Wei, Vladislav V. Klepov, Henry F. Schaefer III and Gregory H. Robinson*, 
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引用次数: 0

摘要

通过立体要求极高的二硫代二亚乙基锂自由基(2)与碘化铝的低温反应,实验性地得到了稳定的三(二硫代二亚乙基)三辐射铝(3)。化合物 3 的特征通过单晶 X 射线衍射、紫外-可见光光谱、EPR 光谱、SQUID 磁力计和理论计算得以确定。变温连续波 EPR 实验和 SQUID 磁力测定法明确证实了三元化合物 3 的四元基态。SQUID 磁力测定法和打破对称的 DFT 计算都揭示了一个较小的双四元能隙 [ΔEDQ = 0.18 kcal mol-1 (SQUID); ΔEDQ = 0.14 kcal mol-1 (DFT)]。脉冲 EPR 实验(电子自旋回波包络调制)进一步证明了这些二硫环戊烯基自由基与 3 的中心铝核之间的相互作用。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

A Stable Aluminum Tris(dithiolene) Triradical

A Stable Aluminum Tris(dithiolene) Triradical

A Stable Aluminum Tris(dithiolene) Triradical

A stable aluminum tris(dithiolene) triradical (3) was experimentally realized through a low-temperature reaction of the sterically demanding lithium dithiolene radical (2) with aluminum iodide. Compound 3 was characterized by single-crystal X-ray diffraction, UV–vis and EPR spectroscopy, SQUID magnetometry, and theoretical computations. The quartet ground state of triradical 3 has been unambiguously confirmed by variable-temperature continuous wave EPR experiments and SQUID magnetometry. Both SQUID magnetometry and broken-symmetry DFT computations reveal a small doublet–quartet energy gap [ΔEDQ = 0.18 kcal mol–1 (SQUID); ΔEDQ = 0.14 kcal mol–1 (DFT)]. The pulsed EPR experiment (electron spin echo envelop modulation) provides further evidence for the interaction of these dithiolene-based radicals with the central aluminum nucleus of 3.

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来源期刊
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.
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