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*,
{"title":"稳定的三(二硫环戊烯)三烷基铝","authors":"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*, ","doi":"10.1021/jacs.4c05631","DOIUrl":null,"url":null,"abstract":"<p >A stable aluminum tris(dithiolene) triradical (<b>3</b>) was experimentally realized through a low-temperature reaction of the sterically demanding lithium dithiolene radical (<b>2</b>) with aluminum iodide. Compound <b>3</b> was characterized by single-crystal X-ray diffraction, UV–vis and EPR spectroscopy, SQUID magnetometry, and theoretical computations. The quartet ground state of triradical <b>3</b> 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<i>E</i><sub>DQ</sub> = 0.18 kcal mol<sup>–1</sup> (SQUID); Δ<i>E</i><sub>DQ</sub> = 0.14 kcal mol<sup>–1</sup> (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 <b>3</b>.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"146 23","pages":"16340–16347"},"PeriodicalIF":15.6000,"publicationDate":"2024-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacs.4c05631","citationCount":"0","resultStr":"{\"title\":\"A Stable Aluminum Tris(dithiolene) Triradical\",\"authors\":\"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*, \",\"doi\":\"10.1021/jacs.4c05631\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A stable aluminum tris(dithiolene) triradical (<b>3</b>) was experimentally realized through a low-temperature reaction of the sterically demanding lithium dithiolene radical (<b>2</b>) with aluminum iodide. Compound <b>3</b> was characterized by single-crystal X-ray diffraction, UV–vis and EPR spectroscopy, SQUID magnetometry, and theoretical computations. The quartet ground state of triradical <b>3</b> 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<i>E</i><sub>DQ</sub> = 0.18 kcal mol<sup>–1</sup> (SQUID); Δ<i>E</i><sub>DQ</sub> = 0.14 kcal mol<sup>–1</sup> (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 <b>3</b>.</p>\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":\"146 23\",\"pages\":\"16340–16347\"},\"PeriodicalIF\":15.6000,\"publicationDate\":\"2024-05-31\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/jacs.4c05631\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/jacs.4c05631\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacs.4c05631","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
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.
期刊介绍:
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