Rolling two-dimensional covalent organic framework (COF) sheets into one-dimensional electronic and proton-conductive nanotubes

Mimicking the interconvertible carbon allotropes of 2-dimensional (2D) graphene and 1-dimensional (1D) carbon nanotubes (CNTs), herein we report the in situ transformation of 2D π-conjugated covalent organic frameworks (COFs) sheet into 1D nanotubular structures via self-assembly the sheets at solvent interfaces. The facile “roll-sheets” self-assembly resulted in coaxial nanotubes with uniform cross-sectional diameter, which was realized for diazapyrene-based COFs but not for the corresponding pyrene COF, although both possess similar chemical structures. Upon replacing the carbon atoms at 2,7-positions of pyrene with nitrogen, contrasting optical and electronic properties were realized, reflecting the rolled structure of the conjugated 2D sheets. The nanotubes exhibited concerted electronic- and proton-conducting nature with stable conducting pathways at ambient conditions. The nitrogen centers act simultaneously as the site for charge carrier doping and proton acceptors, as evidenced by the high photo- and electrical conductivity, as well as the record proton conductivity (σ = 1.98 S cm −1 ) results. The present diazapyrene-based 1D nanotubular COF serves as a unique materials platform with electronic conduction in the wall and proton conduction in the core, respectively.