Design, synthesis, and structure of versatile supramolecular building blocks

The hydrogen bonding hierarchy is a set of guidelines that describe the way different functional groups interact by themselves and in the presence of other functional groups. This dissertation is devoted to examining this set of rules with a view to refining supramolecular synthesis.; The supramolecular solid-state behavior of boronic acids has been probed via a synthetic and crystallographic study. 4-Methylphenyl boronic acid often crystallized by itself in preference to forming co-crystals with N-heterocycles (co-crystal formation = 29%). When co-crystals did form, (B)O-H···N hydrogen bonds were observed. With 4-carboxyphenyl boronic acid and organic bases (co-crystal formation = 80%), the boronic acid steadfastly interacted with a carboxylate instead of forming boronic acid dimers.; 4/5-Pyrimidine carboxylic acids were synthesized, characterized via 1H NMR, IR and X-ray crystallography and used as ligands in coordination chemistry; both ligands display very reliable coordination modes based on seven crystal structures. The carboxylic acid was always deprotonated, eliminating the need for potentially disruptive counterions. The 4-pyrimidine carboxylic acid always coordinated to the metal via an N(3) - carboxylate chelate, similar to picolinate. The 5-pyrimidine carboxylic acid coordinated via only one nitrogen atom in every case, making it more reliable than its pyridine analogs nicotinate and isonicotinate.; Four extended pyridine oximes containing an imine linkage were synthesized, characterized via 1H NMR and IR spectroscopy and used for co-crystallization experiments. We sought to organize binary carboxylic acid-pyridine-based supermolecules using oxime-oxime dimers as the secondary interaction. Based on three crystal structures, the primary interaction was found to be a carboxylic acid - pyridine hydrogen bond. The carbonyl moiety proved to be the second-best hydrogen-bond acceptor and formed O-H···O hydrogen bonds with the oxime, leading to tetrameric supermolecules.; We synthesized and characterized a series of asymmetric bipyridine molecules with fluoro-, methoxy- and carboxamide substituents and successfully prepared approximately 110 co-crystals, four of which were crystallographically characterized. We also prepared and characterized 2-(3/4pyridyl)-benzimidazole, which were also used in co-crystallization experiments with the 3-isomer giving a 56% supramolecular yield and the 4-isomer giving a 89% supramolecular yield. The supramolecular connectivity, an O-H···N hydrogen bond between a carboxylic acid and pyridine, displayed an 80% yield.