The oxime functionality and the construction of supramolecular hydrogen-bonded architectures: A crystal-engineering approach

The controlled assembly of 3-D molecular or ionic solids from the chaos of the solution phase represents a task of immense proportion. This dissertation demonstrates how the principles of crystal engineering may be used to gain topological control over molecules/ions in the solid-state. Using a stepwise approach, molecular and ionic oxime-functionalized ‘building blocks’ were used to predictably assemble both organic and inorganic/organic hybrid materials into ordered, hydrogen-bonded networks.; Herein, we report the syntheses and single-crystal X-ray structures of a variety of aliphatic and aromatic oximes. The aliphatic oximes showed a multitude of hydrogen-bonding patterns, thus making them unsuitable for a crystal engineering design strategy. However, the aromatic oximes consistently assembled infinite, hydrogen-bonded chains, making them ideal for the rational design of hydrogen-bonded architectures.; Synthesis of a variety of pyridine oximes afforded molecules capable of simultaneous metal coordination and self-complementary hydrogen bonding. Crystallographic analysis of the free molecules showed the oxime O-H to preferentially hydrogen bond with the pyridine nitrogen atom instead of the oxime nitrogen atom to generate infinite 1-D chains.; Use of the pyridine oximes as ligands with Ag(I), Ni(II), and Cu(I) ions demonstrated the ability of the oxime moiety for directing the assembly of metal complexes into ordered, hydrogen-bonded networks, where the preferred coordination geometry of the metal ion dictated the topology of the resulting structure.; Synthesis and structural characterization of four new (pyridylmethylene)aminoacetophenone oximes allowed for the examination of the effects of increasing the separation between the oxime moiety and the pyridine nitrogen atom. These ‘extended’ oximes displayed the same solid-state behavior as their shorter analogues, the pyridine oximes. Furthermore, use of the (pyridylmethylene)aminoacetophenone oximes in the syntheses of a variety of silver(I) complexes effectively ‘extended’ the resulting hydrogen-bonded network and promoted the inclusion of solvent into the lattice.; Finally, we explored the deliberate assembly of lamellar inorganic/organic hybrid materials based on a combination of 1-D coordination polymers and intermolecular hydrogen bonds. Use of an infinite coordination polymer with known topology as a synthetic module facilitated intermolecular synthesis.