A Doubly Twisted Molecular Nanocarbon With Substantial π-Overlap: Facile Synthesis, Chiral Resolution, and Through-Space Electronic Coupling

Twisted molecular nanocarbons (TMNCs) represent attractive targets due to their persistent chirality and potential through-space electronic interactions, which remain largely unrevealed. Herein we report an efficient synthesis of a figure-eight TMNC 1 with substantial π-overlap, by using a quantitative, four-fold regioselective Scholl reaction. The (P,P)- and (M,M)- enantiomers can be readily separated by preparative TLC plate, enabling persistent chiroptical properties with moderate dissymmetric factors (|g_abs| = 3.5 × 10⁻³ and |g_lum| = 8.1 × 10⁻³). Crystallographic analysis reveals a compressed lemniscular scaffold of TMNC 1 with close intramolecular π–π contacts (2.887–3.386 Å). Racemic crystals pack via C–H···π interactions, whereas enantiopure (M,M)-1 form tightly stacked π-dimers. Notably, the dication 1²⁺ exhibits pronounced spin polarization and through-space electronic interactions between the overlapped pyrene units, manifesting characteristic spatial aromaticity. This work establishes a versatile platform for exploring through-space electronic communication in topological nanocarbons.