Functionalized macrocyclic ligands: Synthesis, self-assembly, and solid-state characterization

This thesis focuses on the synthesis of functionalized, cross-conjugated macrocycles that possess fascinating structural features and tunable properties. Through appropriate derivatization, macrocyclic species with desirable characteristics may be realized, including the ability to interact with transition metals and aggregate such that channel-containing structures are formed.; To understand the effects of substitution pendant to the macrocyclic core, several cross-conjugated macrocycles were prepared, based on the incorporation of ortho-, meta-, and para-diethynylbenzene. Macrocycles featuring diethynylpyridine installed within the enyne core, directed in either an exo- or endotopic fashion, were also synthesized, suitable for coordination to a transition metal.; The coordinative ability of these porous 4,4'-bipyridine analogues was established through the synthesis of porphyrinic supramolecular assemblies. The structural and electronic properties of these species were evaluated to provide a description of the scope and limitations of the supramolecular building blocks. X-ray crystallographic analysis of these species demonstrated their ability to form highly-ordered, porous solids.; The macrocyclic enyne core of these species was elaborated by incorporation of metal acetylide linkage(s) that provided ligands with expanded pores and greater solubility. The coordinative ability of these platinacycles was demonstrated by preparing coordination complexes, and an examination of the solid-state structural properties of the ligands and their complexes was achieved. The electronic and nonlinear optical properties of several species were also examined.; Through treatment with a metal salt, the pyridine-containing macrocycles were found to stack in the solid-state to create two sets of large, perpendicular channels, as confirmed through X-ray crystallographic analysis. Recent efforts have focused on the study of these materials using hyperpolarized 129Xe NMR spectroscopy. It was established that these materials retain their porosity in the absence of co-crystallized solvent. Furthermore, 129Xe NW spectroscopy provides insight into the pore structure of channel-containing organic materials.; Investigations into "cross-linking" of the pyridine-containing platinacycles led to the discovery that treatment of a trans-acetylide complex with a chelating diphosphine affords formation of the cis -chelated analogue. This methodology was established through the preparation of several cis-acetylide complexes and the applicability of this strategy to the preparation of chiral metal acetylide complexes and chiral macrocycles has been developed.