Reversal of Clar's Aromatic‐Sextet Rule in Ultrashort Single‐End‐Capped [5,5] Carbon Nanotubes

Abstract

Abstract The three‐fold HOMO‐LUMO gap oscillation, typical of finite length armchair carbon nanotubes (CNT), has a major effect on the magnetic response of ultrashort, single‐end‐capped [5,5] carbon nanotubes to a perturbing magnetic field parallel to the main symmetry axis. For the CNT's containing 40, 70, and 100 carbon atoms, for which 100 % of the C=C double bonds can be grouped into aromatic‐sextets, i. e., fully or complete Clar networks, large paratropic (antiaromatic) global circulations around the cylindrical axis are predicted at the DFT level of calculation. Local and semi‐global diatropic (aromatic) currents of strengths not larger than that of the benzene molecule are determined for a perpendicular perturbing magnetic field. CNTs of intermediate lengths do not display this enhanced antiaromatic response. The paratropic current flow clearly shows that these complete Clar networks can be viewed as stacked cycloparaphenylene belts, each providing a double 4n annulene circuit as a consequence of the quinoidal resonance structure that results from their closure. Paradoxically, the fully aromatic Clar structure itself is responsible for the enhanced global antiaromaticity.

Keywords

• aromaticity
• density functional calculations
• magnetic properties
• nanotubes
• cycloparaphenylene