The application of arylamines as redox auxiliaries, polar crystals, and organic semiconductors

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dc.contributor LeClair, Patrick R.
dc.contributor Nikles, David E.
dc.contributor Shaughnessy, Kevin H.
dc.contributor Snowden, Timothy S.
dc.contributor.advisor Blackstock, Silas C. Gray, Lester Trummer 2017-03-01T16:34:04Z 2017-03-01T16:34:04Z 2012
dc.identifier.other u0015_0000001_0000975
dc.identifier.other Gray_alatus_0004D_11244
dc.description Electronic Thesis or Dissertation
dc.description.abstract Arylamines and derivatives thereof have been developed for use in several applications. Among these include: the development of an arylamine moiety to act as a trigger and redox catalyst for an organic reaction, the use of a specific arylamine moiety as a synthon in the preparation of a series of polar organic crystalline materials, and a preliminary investigation of an arylamine salt as a potential organic semiconductor. The synthesis of novel norbornadiene (N) derivatives with appended redox-auxiliary (RA) units for use as switchable photoelectrochromic materials is reported. The photochemical and electrochemical properties are investigated by UV-vis spectroscopy, chemical actinometry, and cyclic voltammetry. The pendant RA functions as a stable redox unit capable of catalyzing the conversion of the N form to the quadricyclane (Q) form, releasing stored ring-strain energy as heat. Aside from demonstrating the principle of RA catalysis, the new N derivatives demonstrate possible utility as recyclable solar fuels or as photo-electrical switchable systems for informational or mechanical applications at the molecular level. A second project involving the preparation of a series of m-phenylenediamine derivatives which assemble (crystallize) preferentially with polar order is described. The crystal structures of these analogs have been elucidated by X-ray crystallography, and their crystalline properties explored by differential scanning calorimetry. Insight gained through this study has led to a greater understanding of the requirements for polar ordering of these molecules, allowing for the rational design of certain polar organic crystals derived from such structures. Finally, a preliminary study of the structure and properties of radical cation and dication salts of tetra(p-anisyl)-p-phenylenediamine (TAPD), which show promise for use as organic one-electron oxidants and as organic semiconductors, is presented. The preparation and characterization of TAPD salts is described. Their electrochemical properties have been explored by powder pellet I-V electrochemical measurements.
dc.format.extent 260 p.
dc.format.medium electronic
dc.format.mimetype application/pdf
dc.language English
dc.language.iso en_US
dc.publisher University of Alabama Libraries
dc.relation.ispartof The University of Alabama Electronic Theses and Dissertations
dc.relation.ispartof The University of Alabama Libraries Digital Collections
dc.relation.hasversion born digital
dc.rights All rights reserved by the author unless otherwise indicated.
dc.subject.other Chemistry
dc.title The application of arylamines as redox auxiliaries, polar crystals, and organic semiconductors
dc.type thesis
dc.type text University of Alabama. Department of Chemistry Chemistry The University of Alabama doctoral Ph.D.

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