Acetal-functionalized encaged copper(I) complexes and polymer encapsulated reverse micelle composites

Abstract

This work describes synthetic methods for encaging coordination complexes within ligand frameworks and polymer encapsulated reverse micelle composites. Caging coordination complexes in this manner can preserve some facets of the complexes' chemical identity and behavior while simultaneously changing others. Chapter 1 considers the methodologies employed towards preparing encaged copper(I) complexes through performing interligand cyclizations with diacetal-derivitized 5,5'-dicarboxaldehyde-2,2'-bipyridine bischelated precursor complexes ([CuI(NN)2]X). Encaging copper(I) protects it both from oxidation and from axially directed nucleophilic attack. The prepared copper(I) complexes displayed long emission lifetimes (> 0.50 μs), thus enabling them to store and ultimately transfer both electrons and energy. Chapter 2 addresses many unresolved issues surrounding the production of tris(bipyridine)ruthenium(II) chloride ([Ru(bpy)3]Cl2) chromophore-sequestered polymer encapsulated reverse micelle composite (PERMC) materials. Styrene:divinylbenzene composite precursor reverse micellar solution (CPRMS) nonpolar phases are polymerized in order to prepare the PERMC materials. Desired 'bulk solution-like behavior' of the sequestered polar chromophores is realized upon their PERMC sequestration. Chapter 3 presents the conclusion of research performed on phenoxazine (POZ) donor-based Donor-Chromophore-Acceptor (D-C2+-A2+, or triad)-sequestered PERMC materials. Triad-sequestered PERMCs can serve as optically addressable solid-state sensors for the detection of external magnetic fields. Upon triad photoexcitation, a series of electron transfer steps occurs which produces a spectroscopically detectable triplet biradical Charge Separated State (3CSS, D+·-C2+-A+·) but only in solution. The 3CSS lifetimes (less) of the sequestered triads lengthen and become biexponential in quality as magnetic field strength increases. Such behavior constitutes a magnetic field effect (MFE). The composite nature of the PERMCs allows for such MFEs to be detected. Chapter 4 provides a forum for the introduction of [Ru(bpy)3]Cl2 chromophore-sequestered PERMCs of the following cationic, zwitterionic, and anionic surfactant:cosurfactant systems: cetyltrimethylammonium bromide: 1-octanol (1 CTAB: 5 CsOH), cetyldimethylbenzylammonium bromide (CDBA), hexadecylpyridinium bromide (HDPB), phosphatidylcholine extracted from soy lecithin, and Aerosol-OT:trioctylphosphine oxide (3 AOT:2 TOPO). Chapter 5 builds on the above work by characterizing POZ donor-based triad-sequestered PERMC magnetic field sensors of different surfactant:cosurfactant systems.