Hydrogen‐Bonding‐Regulated Supramolecular Nanostructures and Impact on Multivalent Binding

: Herein we describe the H-bonding-regulated nanostructure, thermodynamics, and multivalent binding of two bolaamphiphiles NDI-1 and NDI-2 consisting of a hydrophobic naphthalene diimide connected to a hydrophilic wedge by a H-bonding group and a glucose moiety on its two arms. NDI-1 and NDI-2 differ by the single H-bonding group, namely, hydrazide or amide, which triggers the formation of vesicles and cylindrical micelles, respectively. Although the extended H-bonding ensures stacking with head-to-head orientation and the formation of an array of the appended glucose moieties in both systems, the adaptive cylindrical structure exhibited superior multivalent binding with concanavalin A (ConA) to that of the vesicle. A control amphiphile lacking a H-bonding group assembled with a random lateral orientation to produce spherical micelles without any notable multivalent binding.