Three sets of polyoxometalates (POM)-based amphiphilic hybrid macromolecules are used as model to understand the effect of rigidity in the self-assembly process. Anderson T-shape-linked oligo fluorene (Anderson-TOF<sub>4</sub>) and Dawson-TOF<sub>4</sub> are observed to self-assemble into the onion-like vesicles and the multi-layer vesicles, respectively, as confirmed by Laser Light Scattering (LLS), Transmission Electron Microscopy (TEM). Interestingly, they show self-recognition behavior by forming individual assemblies in the mixed solution. The multi-layered structures are in the basis of the rigidity of the hydrophobic blocks of the amphiphiles. While the charged hydrophilic clusters introduce the counterion-mediated attraction, which plays an important role in the inter-layer attraction. The hydrophobic blocks with different rigidity are introduced: partially rigid polystyrene (PS) and fully flexible alkyl chain. However, the self-recognition behaviors are not found in these two systems because the lack of rigidity. Studies reveal the importance of rigidity in the self-assembly process and suggest the potential of rigid amphiphilic hybrid in geometry-directed self-assembly.

Geometry-directed self-recognition in giant amphiphiles

ACS Spring 2022

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