Cooperative, anti-cooperative, and synergistic supramolecular interactions mediate self-organization of self-assembling dendrons, dendrimers, and dendronized macromolecules

After a brief discussion of the discovery of covalent and self-organizable dendrons, dendrimers, and dendronized macromolecules, examples of cooperative, anti-cooperative and synergistic supramolecular-interactions mediating self-assembly and self-organization of supramolecular dendrimers will be presented. Dendronized crown-ethers will be used to demonstrate these interactions generated by cation-dipole, π–π stacking, H-bonding, fluorination, the specialty of Professor Giuseppe Resnati celebrated with this occasion, and covalent macromolecular interactions. It will be demonstrated that fluorination of self-assembling dendrons generates a simple approach to dendronized donors and acceptors and of their donor-acceptor complexes. The evolution of helical chirality from its discovery in tobacco mosaic virus-like supramolecular dendrimers to helical-globular-dendrimers producing chiral Frank-Kasper and quasicrystal periodic and quasiperiodic arrays will be highlighted. Helical Aquaporin-like transmembrane proteins and spherical containers will be assembled from dendritic dipeptides by a combination of H-bonding and aromatic π–π interactions. The work of Giulio Natta will be honored by a discussion of the dendronized helical stereoisomers of poly(phenylacetylene) and their intramolecular electrocyclization. Polymer chemistry will be employed as a tool to support the quasi-equivalence of self-assembling dendrons and elaborate their shape inversion from helical spheres to helical columns. Helical supramolecular dendrimers induce a helical conformation into atactic-polymer backbones, a dream which even Giulio Natta could not think of. Hydrophobic, H-bonding and ion-ion interactions generated self-assembling amphiphilic Janus dendrimers and glycodendrimers which mimic cell membranes, their glycans, and provide one-component multifunctional sequence-defined ionizable amphiphilic Janus dendrimers which target the delivery of mRNA to specific organs for stable vaccines and therapeutics. • Dendrons, dendrimers, and dendronized polymers self-organize helical arrays. • Helical columnar and globular supramolecular dendrimers. • Cooperative, anti-cooperative and synergistic supramolecular interactions. • Supramolecular ionic, electronic, and water channels. • Supramolecular orientational memory effect yields unprecedented helical arrays.