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Closed\u2010shell neutral double helices, 1\u2010TMS<jats:sub>12<\/jats:sub> and 2\u2010TMS<jats:sub>8<\/jats:sub>, have nearly identical first oxidation potentials, <jats:italic>E<\/jats:italic>\n<jats:sup>+\/0<\/jats:sup>\u2009\u2248\u2009+1.33\u2009V, corresponding to reversible oxidation to their radical cations. The radical cations are generated, using tungsten hexachloride in dichloromethane (DCM) as an oxidant, <jats:italic>E<\/jats:italic>\n<jats:sup>+\/0<\/jats:sup>\u2009\u2248\u2009+1.56\u2009V. EPR spectra consist of a relatively sharp singlet peak with an unusually low <jats:italic>g<\/jats:italic>\u2010value of 2.001\u20132.002, thus suggesting exclusive delocalization of spin density over \u03c0\u2010conjugated system consisting of carbon atoms only. DFT computations confirm these findings, as only negligible fraction of spin density is found on sulfur and silicon atoms and the spin density is delocalized over a single tetrathiophene moiety. For radical cation, 1<jats:sup>\u2022+<\/jats:sup>\u2010TMS<jats:sub>12<\/jats:sub>, energy level of the singly occupied molecular orbital (SOMO) lies below the four highest occupied molecular orbitals (HOMOs), thus indicating the SOMO\u2013HOMO inversion (SHI) and therefore, violating the Aufbau principle. 1<jats:sup>\u2022+<\/jats:sup>\u2010TMS<jats:sub>12<\/jats:sub> has a half\u2010life of the order of only 5\u2009min at room temperature. EPR peak intensity of 2<jats:sup>\u2022+<\/jats:sup>\u2010TMS<jats:sub>8<\/jats:sub>, which does not show SHI, is practically unchanged over at least 2\u2009h.<\/jats:p>","DOI":"10.1111\/php.13475","type":"journal-article","created":{"date-parts":[[2021,6,21]],"date-time":"2021-06-21T14:57:04Z","timestamp":1624287424000},"page":"1376-1390","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":17,"title":["Thiophene\u2010Based Double Helices: Radical Cations with SOMO\u2013HOMO Energy Level Inversion<sup>\u2020<\/sup>"],"prefix":"10.1111","volume":"97","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8856-1536","authenticated-orcid":false,"given":"Andrzej","family":"Rajca","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Nebraska  Lincoln NE USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chan","family":"Shu","sequence":"additional","affiliation":[{"name":"Department of Chemistry 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