nn7b06376_si_001.pdf (7.79 MB)
Controlled Self-Assembly of Photofunctional Supramolecular Nanotubes
journal contribution
posted on 2017-12-19, 00:00 authored by Erez Cohen, Haim Weissman, Iddo Pinkas, Eyal Shimoni, Pavel Rehak, Petr Král, Boris RybtchinskiDesigning
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 via 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 via 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 via 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.
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bipyridine linkerinsightsection geometryMolecular dynamics simulationsphotonic propertiesPhotofunctional Supramolecular Nanotubes Designing supramolecular nanotubesSNT self-assembly advance design approacheselectron delocalizationControlled Self-Assembly5 nmbuilding blocksperylene diimide moietiescontrol strategiesphotoinduced charge separation3 nmassembly conditionsPEG chain lengthSNT self-assemblyside chainspolyethylene glycolbis-aromatic cores
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