Sapphyrins : aggregation and anion binding behavior in polar, protic media
Abstract
Sapphyrin was the first expanded porphyrin to be reported in the literature
and remains among the most extensively studied of all expanded porphyrins.
Much of the interest in this macrocycle reflects its ability to bind anions, a
phenomenon that has been examined in solution and in the solid state by a wide
range of experimental techniques. The first chapter of this dissertation provides a
history of the anion binding chemistry of the sapphyrins, as well as a review of
the synthetic methodologies employed to make them. The second chapter builds
upon this work by examining the interactions of several water soluble sapphyrins
with phosphate and chloride anions in aqueous media. The binding of phosphate
and chloride anions in this milieu was found to be closely related to the
aggregation state of sapphyrin, the study of which by optical spectroscopic
techniques is also discussed in Chapter 2. In order to study the aggregation
behavior of sapphyrins further, several 10,15-diaryl sapphyrins were prepared.
The preparation and characterization of these systems is discussed in Chapter 3.
The dimerization constants of these systems were measured in methanol, and a
preliminary study of their anion binding behavior in organic solvents was
performed. Finally, in Chapter 4, the synthesis of a new bipyrrole is laid out and
several sapphyrin systems that could be prepared from this precursor are
proposed. Future directions for the work described in this dissertation are also
presented in this chapter. Experimental methods and characterization data for
compounds synthesized by the author are presented in Chapter 5.
Department
Description
text