No abstract

Hierarchical organization of self-assembled structures into superstructures is omnipresent in Nature but has been rarely achieved in synthetic molecular assembly due to the absence of clear structural rules.W eh erein report on the selfassembly of scissor-shaped azobenzene dyads which form discrete nanotoroids that further organizei nto 2D porous networks.T he steric demand of the peripheral aliphatic units diminishes the trend of the azobenzene dyad to constitute stackable nanotoroids in solution, thus affording isolated (unstackable) nanotoroids upon cooling. Upon drying, these nanotoroids organizea tg raphite surface to form well-defined 2D porous networks.The photoirradiation with UV and visible light enabled reversible dissociation and reconstruction of nanotoroids through the efficient trans$cis isomerization of azobenzene moieties in solution.

Recent advances in the research field of supramolecularly engineered dye aggregates have enabled the design of simple one-dimensional stacks such as fibers and of closed structures such as nanotoroids (nanorings). More...

The amplification of molecular asymmetry through self-assembly is a phenomenon that not only comprehends the origin of homochirality in nature but also produces chiroptically active functional materials from molecules with minimal enantiomeric purity. Understanding how molecular asymmetry can be transferred and amplified into higher-order structures in a hierarchical selfassembly system is important but still unexplored. Herein, we present an intriguing example of the amplification of molecular asymmetry in hierarchically self-assembled nanotubes that feature discrete and isolatable toroidal intermediates. The hierarchical self-assembly is initiated via asymmetric intramolecular folding of scissor-shaped azobenzene dyads furnished with chiral side chains. When scalemic mixtures of the enantiomers are dissolved in a non-polar solvent and cooled to 20 °C, single-handed nanotoroids are formed, as confirmed using atomic force microscopy and circular dichroism analyses. A strong majority-rules effect at the nanotoroid level is observed and can be explained by a low mismatch penalty and a high helix-reversal penalty. The single-handed nanotoroids stack upon cooling to 0 °C to exclusively afford their respective single-handed nanotubes. Thus, the same degree of amplification of molecular asymmetry is realized at the nanotube level. The internal packing efficiency of molecules within nanotubes prepared from the pure enantiomers or their scalemic mixtures is likely different, as suggested by the absence of higher-order structure (supercoil) formation in the latter. Xray diffraction analysis of the anisotropically oriented nanotube films revealed looser molecular packing within the scalemic nanotubes, which clearly reflects the lower enantiomeric purity of their internal chiral side chains.

Unique relationships between hierarchically organized biological nanostructures and functions have motivated chemists to construct sophisticated artificial nanostructured systems from small and simple synthetic molecules through self-assembly. As one of such sophisticated systems, we have investigated scissor-shaped photochromic dyads that can hierarchically selfassemble into discrete nanostructures showing photoresponsive properties. We synthesized various azobenzene dyads and found that these dyads adopt intramolecularly folded conformation like a closed scissor, and then self-assemble into toroidal nanostructures by generating curvature. The toroids further organize into nanotubes and further into helical supramolecular fibers depending on the nature of alkyl substituents. All of these nanostructures can be dissociated and reorganized through the photoisomerization of azobenzene units. On the other hand, the introduction of stilbene chromophores instead of azobenzenes leads to onedimensional supramolecular polymerization, which upon the intramolecular photocyclization of stilbene chromophores shifts to curved self-assembly leading to helicoidal fibers with distinct supramolecular chirality.