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X\u2010ray crystallography revealed finely\u2010tuned packing and helix assemblies of the radicals by the size of chiral substituents in crystalline state. In accordance with the crystalline\u2010state packing, the powder ESR spectra indicate that <jats:bold>4\u2009a<\/jats:bold><jats:sup>\u2212<\/jats:sup>\u22c5CoCp<jats:sub>2<\/jats:sub><jats:sup>+<\/jats:sup> and <jats:bold>4\u2009c<\/jats:bold><jats:sup>\u2212<\/jats:sup>\u22c5CoCp<jats:sub>2<\/jats:sub><jats:sup>+<\/jats:sup> \u03c0\u2010dimers exhibit thermally excited triplet states arising from strong spin\u2010spin interactions, while discrete <jats:bold>4\u2009b<jats:sup>\u2212<\/jats:sup><\/jats:bold>\u22c5CoCp<jats:sub>2<\/jats:sub><jats:sup>+<\/jats:sup> shows a broad doublet\u2010state signal reflecting weak spin\u2010spin interactions. The interplay between the unpaired electron spin and chiral substituents was studied by UV\u2010Vis\u2010NIR spectra, electronic circular dichroism (ECD) and TD DFT calculations. Different NIR absorptions of the radicals attributing to isolated SOMO\u2192LUMO+1 (~889\u2005nm) transitions were recorded. The emergence of Cotton effects (CEs) at the NIR region for <jats:bold>4\u2009c<\/jats:bold><jats:sup>\u2212<\/jats:sup>\u22c5CoCp<jats:sub>2<\/jats:sub><jats:sup>+<\/jats:sup> radical enantiomers suggest the interplay between chirality and unpaired electron spin. The origin of the different circularly polarized light absorptions regarding SOMO derived transitions (around 880\u2005nm) was attributed to chiral substitutes regulated electric and magnetic transition dipole moments of the unpaired electron participated transition.<\/jats:p>","DOI":"10.1002\/chem.202302954","type":"journal-article","created":{"date-parts":[[2023,10,30]],"date-time":"2023-10-30T23:16:03Z","timestamp":1698707763000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Chiral Benzene Triimide (BTI) Radical Anions for Probing the Interplay of Unpaired Electron Spin and Chirality"],"prefix":"10.1002","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2604-3642","authenticated-orcid":false,"given":"De\u2010Hui","family":"Tuo","sequence":"first","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences CAS Key Laboratory of Molecular Recognition and Function Institute of 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