Ligand Tail Controls the Conformation of Indium Sulfide Ultrathin Nanoribbons

We report the conformational control of 2D ultrathin indium sulfide nanoribbons by tuning their amine ligands' alkyl chain. The initial orthorhombic InS nanoribbons bare n-octylamine ligands and display a highly curved geometry with a characteristic figure of eight shapes. Exchanging the native ligand by oleylamine induces their complete unfolding to yield flat board-shaped nanoribbons. Significant strain variations in the InS crystal structure accompany this shape-shifting. By tuning the linear alkyl chain length from 4 to 18 carbon atoms, we show using small-angle X-ray scattering in solution and transmission electron microscopy that the curvature of the nanoribbon subtly depends on the ligand-ligand interactions at the nanoribbon's surface. The curvature decreases gradually as the chain length increases, while carbon unsaturation has an unexpectedly significant effect at constant chain length. These experiments shed light on the critical role of the ligand monolayer on the curvature of ultrathin 2D crystalline nanosheets and demonstrate that weak supramolecular forces within the organic part of colloidal nanocrystals can dramatically impact their shape. This transduction mechanism, in which changes in the organic monolayer impact the shape of a nanocrystal, will help to devise new strategies to design stimuli-responsive systems that take advantage of both the flexibility of organic moieties and the physical properties of the inorganic core.