Controlled Self-Assembly of Photofunctional Supramolecular Nanotubes Erez Cohen Haim Weissman Iddo Pinkas Eyal Shimoni Pavel Rehak Petr Král Boris Rybtchinski 10.1021/acsnano.7b06376.s001 https://acs.figshare.com/articles/journal_contribution/Controlled_Self-Assembly_of_Photofunctional_Supramolecular_Nanotubes/5733723 Designing supramolecular nanotubes (SNTs) with distinct dimensions and properties is highly desirable, yet challenging, since structural control strategies are lacking. Furthermore, relatively complex building blocks are often employed in SNT self-assembly. Here, we demonstrate that symmetric bolaamphiphiles having a hydrophobic core comprised of two perylene diimide moieties connected <i>via</i> a bipyridine linker and bearing polyethylene glycol (PEG) side chains can self-assemble into diverse molecular nanotubes. The structure of the nanotubes can be controlled by assembly conditions (solvent composition and temperature) and a PEG chain length. The resulting nanotubes differ both in diameter and cross section geometry, having widths of 3 nm (triangular-like cross-section), 4 nm (rectangular), and 5 nm (hexagonal). Molecular dynamics simulations provide insights into the stability of the tubular superstructures and their initial stages of self-assembly, revealing a key role of oligomerization <i>via</i> side-by-side aromatic interactions between bis-aromatic cores. Probing electronic and photonic properties of the nanotubes revealed extended electron delocalization and photoinduced charge separation that proceeds <i>via</i> symmetry breaking, a photofunction distinctly different from that of the fibers assembled from the same molecules. A high degree of structural control and insights into SNT self-assembly advance design approaches toward functional organic nanomaterials. 2017-12-19 00:00:00 bipyridine linker insight section geometry Molecular dynamics simulations photonic properties Photofunctional Supramolecular Nanotubes Designing supramolecular nanotubes SNT self-assembly advance design approaches electron delocalization Controlled Self-Assembly 5 nm building blocks perylene diimide moieties control strategies photoinduced charge separation 3 nm assembly conditions PEG chain length SNT self-assembly side chains polyethylene glycol bis-aromatic cores