(375c) Unusual Electronic Properties of Template-Directed ?-Conjugated Porphyrin and Phosphorene Nanotubes

Using large-scale DFT calculations (up to 1476 atoms and 18 432 orbitals), we present the first detailed analysis on the unusual electronic properties of recently synthesized porphyrin¹ and phosphorene nanotubes.² We surprisingly observe extremely large oscillations in the bandgap of these nanostructures as a function of size, in contradiction to typical quantum confinement effects (i.e., the bandgap increases with size in several of these nanotubes). In particular, we find that these intriguing electronic oscillations arise from a size-dependent alternation of aromatic/nonaromatic characteristics in these porphyrin nanotubes. Our analyses of band structures and orbital diagrams indicate that the electronic transitions in these nanostructures are direct-bandgap, optically active “bright” states that can be readily observed in photoelectron spectroscopic experiments. Most importantly due to their unusual bandgap oscillations, we find that both type I and type II donor–acceptor p–n heterojunctions are possible in these template-directed, “bottom-up synthesized” porphyrin nanotubes—a unique property that is not present in conventional carbon nanotubes.

¹S. I. Allec, N. V. Ilawe, and B. M. Wong, “Unusual Bandgap Oscillations in Template-Directed Ï€-Conjugated Porphyrin Nanotubes.” Journal of Physical Chemistry Letters, 7, 2362 (2016)

²S. I. Allec and B. M. Wong, “Inconsistencies in the Electronic Properties of Phosphorene Nanotubes: New Insights from Large-Scale DFT Calculations.” Journal of Physical Chemistry Letters, 7, 4340 (2016)