Revealing the tunability of electronic structures and optical properties of novel SWCNT derivatives, phenine nanotubes.

Single-walled carbon nanotubes (SWCNTs) have evoked great interest for various luminescent applications, but the large emission heterogeneity resulting from the structural complexity of the samples seriously restricts their further development. Herein we theoretically explore the electronic structures and optical properties of phenine nanotubes (pNTs), which are typical luminescent SWCNT derivatives with determined molecular structures that have been synthesized recently (Z. Sun, K. Ikemoto, T. M. Fukunaga, T. Koretsune, R. Arita, S. Sato and H. Isobe, Science, 2019, 363, 151-155; K. Ikemoto, S. Yang, H. Naito, M. Kotani, S. Sato and H. Isobe, Nat. Commun., 2020, 11, 1807). Interestingly, pNTs are found to feature different semiconducting properties to SWCNTs, as indicated by a spatial separation trend in the HOMO and LUMO resulting from periodic structural vacancies. The HOMO-LUMO and optical gaps of pNTs depend inversely on their lengths and diameters, but diameter variation should be an ineffective method for property tuning due to its negligible influence. By contrast, chemical modifications via N doping or hydrogenation highly affect the HOMO-LUMO gaps and their distributions and greatly broaden the light absorption/emission range, and importantly, low-dose hydrogenation is predicted to be a feasible strategy to enhance luminescence. This work, by studying the fundamental photophysical properties of pNTs and making comparisons to SWCNTs, shows the promise of structural vacancy engineering and surface functionalization in acquiring multifunctional tube-like materials.