Diversifying Hierarchical Ionic Assembly by Docking Cations to Anions as Salt Bridges

We expand the diversity of building blocks available for ionic assembly by introducing tertiary (3 degrees) ammonium cations into anion complexes. We use proton transfer between 3 degrees amines and organo-phosphoric acids to generate H-bonding cations (R3NH+) and anions (RHPO4-) that co-assemble with cyanostar macrocycles into assemblies with 2:2:2 stoichiometry. At the heart is a supramolecular dimer where phosphate anions form salt bridges by H-bonding with cations. Unlike conventional 4 degrees ammonium cations, 3,000 commercial amines provide diversity for high-throughput screening of 72 combinations (9 nitrogen bases and 8 acids), producing 13 privileged partners for quantitative assembly. Yields depend on the solvent and sterics of salt bridge formation. Ten more nitrogen bases connect to fluorophores (pyrene), photocatalysts (quinoline), drugs (Cipralex, Zytiga), and ionic liquids (imidazole). The synthesis and examination of 82 new salts exemplify how acid-base chemistry can open a pipeline to a diversity of building blocks for exploring hierarchical ionic assembly.