Tran Phuong M, Wang Yuzhong, Dzikovski Boris, Lahm Mitchell E, Xie Yaoming, Wei Pingrong, Klepov Vladislav V, Schaefer Henry F, Robinson Gregory H
Department of Chemistry and the Center for Computational Chemistry, The University of Georgia, Athens, Georgia 30602-2556, United States.
Department of Chemistry and Chemical Biology, and ACERT, National Biomedical Center for Advanced Electron Spin Resonance Technology, Cornell University, Ithaca, New York 14853-1301, United States.
J Am Chem Soc. 2024 Jun 12;146(23):16340-16347. doi: 10.1021/jacs.4c05631. Epub 2024 May 31.
A stable aluminum tris(dithiolene) triradical () was experimentally realized through a low-temperature reaction of the sterically demanding lithium dithiolene radical () with aluminum iodide. Compound was characterized by single-crystal X-ray diffraction, UV-vis and EPR spectroscopy, SQUID magnetometry, and theoretical computations. The quartet ground state of triradical 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 [Δ = 0.18 kcal mol (SQUID); Δ = 0.14 kcal mol (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 .
通过空间位阻较大的二硫烯锂自由基（ ）与碘化铝的低温反应，实验实现了一种稳定的三（二硫烯）铝三自由基（ ）。化合物 通过单晶X射线衍射、紫外可见光谱和电子顺磁共振光谱、超导量子干涉仪磁力测定以及理论计算进行了表征。变温连续波电子顺磁共振实验和超导量子干涉仪磁力测定明确证实了三自由基 的四重基态。超导量子干涉仪磁力测定和破缺对称性密度泛函理论计算均揭示了一个小的二重态 - 四重态能隙[Δ = 0.18千卡/摩尔（超导量子干涉仪）；Δ = 0.14千卡/摩尔（密度泛函理论）]。脉冲电子顺磁共振实验（电子自旋回波包络调制）为这些基于二硫烯的自由基与 的中心铝核之间的相互作用提供了进一步的证据。
