Strategies for directing aromatic packing

This dissertation explores the design, synthesis, and structure of aromatic molecules with the goal of understanding the forces which affect packing of conjugated molecules in the solid state. Two approaches were applied to direct the assembly of aromatic materials. The first one involved the use of coordination bonds between aromatic nitriles and silver(I) triflate. Several acridine-based ligands were synthesized and crystallized, alone and complexed to silver(I) triflate. Generally, ligands that possessed three peripheral coordination sites formed sheet-like crystal structures. Ligands with only one coordination site crystallized into columnar arrangements with significant edge-to-face interactions. The second approach studied the effect of mutually phobic side-chains on the properties of dyads - molecules comprised of linked electron-rich and electron-poor aromatic moieties. It was shown that, despite attractive electrostatic forces between electron-rich and electron-poor aromatic species, aliphatic hydrocarbon and fluorocarbon side-chains form segregated domains in single crystals. Finally, the mutually phobic side-chain approach was extended to materials based on oligo- or poly-thiophene and naphthalenediimide