Chiral Benzene Triimide (BTI) Radical Anions for Probing the Interplay of Unpaired Electron Spin and Chirality

Abstract Herein a series of chiral BTI radical anions bearing different chiral substituents were efficiently prepared by chemical reduction. X‐ray crystallography revealed finely‐tuned packing and helix assemblies of the radicals by the size of chiral substituents in crystalline state. In accordance with the crystalline‐state packing, the powder ESR spectra indicate that 4 a − ⋅CoCp 2 + and 4 c − ⋅CoCp 2 + π‐dimers exhibit thermally excited triplet states arising from strong spin‐spin interactions, while discrete 4 b − ⋅CoCp 2 + shows a broad doublet‐state signal reflecting weak spin‐spin interactions. The interplay between the unpaired electron spin and chiral substituents was studied by UV‐Vis‐NIR spectra, electronic circular dichroism (ECD) and TD DFT calculations. Different NIR absorptions of the radicals attributing to isolated SOMO→LUMO+1 (~889 nm) transitions were recorded. The emergence of Cotton effects (CEs) at the NIR region for 4 c − ⋅CoCp 2 + 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 nm) was attributed to chiral substitutes regulated electric and magnetic transition dipole moments of the unpaired electron participated transition.