Tetraarylboronic Acid Resorcinarenes: Synthesis, Molecular Recognition, and Templates for the Construction of Three-Dimensional Electronic Organic Materials.
Date of Award
Doctor of Philosophy (PhD)
Robert M. Strongin
The resorcinarenes are remarkable cyclic aromatic tetramers whose impressive impact in the disciplines of molecular recognition, materials science and supramolecular chemistry has been the subject of extensive study and recent review. The potential utility of these materials as chemosensors, catalysts, energy storage and drug delivery agents has been studied or proposed. Research involving resorcinarene molecular containers (careceplexes, carecerands, hemicarcerands) has resulted in landmark achievements including the stabilization of encapusulated cyclobutadiene and benzyne. Functionalization of the resorcinarene lower rim has begun to attract attention as a means to enhance the properties of the parent macrocycles. There has been only one report (1989), however, describing the extension of their lower cavity conjugation. We have performed direct, fourfold conjugation extension of the lower rim. Our findings would allow for the fabrication of heteropolyfunctional, directional molecular scaffolds embodying new receptors and supramolecular materials. We have thus (1) performed a gram scale synthesis and direct isolation of boronic acid functionalized stereoisomeric resorcinarenes; (2) polyfunctionalized at divergent macrocyclic sites, affording chiral and achiral resorcinarene octols and cavitands; (3) presented preliminary evidence that the relatively little-explored C2h resorcinarenes can compete effectively with their C4v counterparts in both covalent and non-covalent binding of polar guests; (4) reported their use in the colorimetric differentiation of carbohydrates; and (5) extended the lower cavity by fourfold aryl coupling under Suzuki conditions.
Lewis, Patrick Tyrone, "Tetraarylboronic Acid Resorcinarenes: Synthesis, Molecular Recognition, and Templates for the Construction of Three-Dimensional Electronic Organic Materials." (2000). LSU Historical Dissertations and Theses. 7372.