Synthesis of Phthalocyanines for Use in Electronic Materials.

Abstract

This dissertation describes the synthesis of phthalocyanines having specialized structures that provide for electrochemical studies of their fundamental properties and/or for direct preparation of phthalocyanine-based electronic materials. Much of the synthetic effort herein is directed toward the development of a particular class of phthalocyanine, herein referred to as benzimidazoporphyrazines. Benzimidazoporphyrazines are desirable substitutes for typical phthalocyanines in applications requiring phthalocyanine-based materials. The value of benzimidazoporphyrazines is derived from their geometry, which provides four substitution positions at peripheral carbon atoms that lie along the N-N axes of the macrocycles. The modular construction of pigment arrays that include phthalocyanines may be greatly facilitated with the use of benzimidazoporphyrazines. The history of research in benzimidazoporphyrazines is brief, and has not heretofore provided access to benzimidazoporphyrazines bearing substituents that may serve as synthetic handles for modification of the pigments after their formation. This report details the development of synthetic methodology to prepare benzimidazoporphyrazines that bear useful synthetic handles. The synthesis of a set of such pigments is also described. Additionally, the new pigments (and one pigment array) are studied with regard to structural confirmation, as well as by photochemical and electrochemical means.