Accommodating Curvature in a Highly Ordered Functionalized Metal Oxide Nanofiber: Synthesis, Characterization, and Multiscale Modeling of Layered Nanosheets

A key element in the rational design of hybrid organic–inorganic nanostructures is control of surfactant packing and adsorption onto the inorganic phase in crystal growth and assembly. In layered single crystal nanofibers and bilayered two-dimensional (2D) nanosheets of vanadium oxide, we show how the chemisorption of preferred densities of surfactant molecules can direct the formation of ordered, curved layers. The atom-scale features of the structures are described using molecular dynamics simulations that quantify surfactant packing effects and confirm the preference for a density of 5 dodecanethiol molecules per 8 vanadium attachment sites in the synthesized structures. This assembly maintains a remarkably well ordered interlayer spacing, even when curved. The assemblies of interdigitated organic bilayers on V2O5 are shown to be sufficiently flexible to tolerate curvature while maintaining a constant interlayer distance without rupture, delamination, or cleavage. The accommodation of curvature and invariant structural integrity points to a beneficial role for oxide-directed organic film packing effects in layered architectures such as stacked nanofibers and hybrid 2D nanosheet systems.