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 1 2+ 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.