Molecular Geometry-Directed Self-Recognition in the Self-Assembly of Giant Amphiphiles

Three sets of polyoxometalate (POM)-based amphiphilic hybrid macromolecules with different rigidity in their organic tails are used as models to understand the effect of molecular rigidity on their possible self-recognition feature during self-assembly processes. Self-recognition is achieved in the mixed solution of two structurally similar, sphere-rigid T-shape-linked oligofluorene(TOF₄ ) rod amphiphiles, with the hydrophilic clusters being Anderson (Anderson-TOF₄ ) and Dawson (Dawson-TOF₄ ), respectively. Anderson-TOF₄ is observed to self-assemble into onion-like multilayer structures and Dawson-TOF₄ forms multilayer vesicles. The self-assembly is controlled by the interdigitation of hydrophobic rods and the counterion-mediated attraction among charged hydrophilic inorganic clusters. When the hydrophobic blocks are less rigid, e.g., partially rigid polystyrene and fully flexible alkyl chains, self-recognition is not observed, attributing to the flexible conformation of hydrophobic molecules in the solvophobic domain. This study reveals that the self-recognition among amphiphiles can be achieved by the geometrical limitation of the supramolecular structure due to the rigidity of solvophobic domains.