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Ultrahigh Density Array of Vertically Aligned Small-molecular Organic Nanowires on Arbitrary Substrates
Published on: June 18, 2013
A Doubly Twisted Molecular Nanocarbon With Substantial π-Overlap: Facile Synthesis, Chiral Resolution, and
Jiawei Shao1, CiHui Lin1, Yuguang Sui1
1Department of Chemistry, State Key Laboratory of Quantum Functional Materials, Southern University of Science and Technology, Shenzhen, China.
None:
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 (|gabs| = 3.5 × 10-3 and |glum| = 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.
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