Sequence‐Mandated, Distinct Assembly of Giant Molecules

Although controlling the primary structure of synthetic polymers is itself a great challenge, the potential of sequence control for tailoring hierarchical structures remains to be exploited, especially in the creation of new and unconventional phases. A series of model amphiphilic chain‐like giant molecules was designed and synthesized by interconnecting both hydrophobic and hydrophilic molecular nanoparticles in precisely defined sequence and composition to investigate their sequence‐dependent phase structures. Not only compositional variation changed the self‐assembled supramolecular phases, but also specific sequences induce unconventional phase formation, including Frank–Kasper phases. The formation mechanism was attributed to the conformational change driven by the collective hydrogen bonding and the sequence‐mandated topology of the molecules. These results show that sequence control in synthetic polymers can have a dramatic impact on polymer properties and self‐assembly. Molekulare Nanopartikel (NPs) können präzise zu kettenartigen Makromolekülen mit vorbestimmter Sequenz aufgereiht werden. Über die Sequenz und Zusammensetzung der synthetischen Polymere lässt sich auch die Struktur ihrer supramolekularen Phase steuern. POSS=polyedrisches oligomeres Silsesquioxan; B hydrophob, D hydrophil.