Date of Award

Winter 12-18-2020

Degree Type

Dissertation

Degree Name

PhD. Chemistry

Department

Chemistry and Biochemistry

Advisor

Sergiu M. Gorun

Committee Member

James Hanson

Committee Member

Stephen Kelty

Keywords

Phthalocyanines, Phthalonitriles, Fluorine substituents, Acylation, Exocyclic conjugation, Photocatalysts

Abstract

Since their discovery at the beginning of the 20th century, phthalocyanines (Pc) have come a long way; today they are replacing the porphyrins (natural products) in most of their applications. The functionalization of the organic macrocycle, the use of different metals, and the change of the axial ligands resulted in Pc applications in a wide range of fields, ranging from photochemistry, paints, catalysis, to fuel cells and cosmetic products.

In Dr. Gorun’s group was developed a series of electron-deficient Pcs that benefit from a Teflon-like chemical shield, meant also to break the π-π interactions, namely the F64PcM series. The present work is focused on (i) the redox properties of complexes with main group trivalent metals, namely non-functionalized F64PcGaCl and F64PcInCl, studied using classical electrochemical methods, cyclic voltammetry, and differential pulse polarography, (ii) the synthesis and photo-catalytical properties of a series of functionalized PcZn, and (iii) heterogenization strategies to produce functionalized Pc-based hybrid materials via bioconjugation or immobilization on solid supports.

Amido phthalonitriles and Pcs were produced to reveal the influence of exocyclic conjugation on the spectroscopic and photochemical properties of the Pcs. The phthalonitrile precursors and Pc, 20 new compounds, were synthesized using conventional and non-conventional methods (microwave), purified by chromatographic techniques, characterized by spectral methods (UV-Vis, FT-IR, 1H-, 19F-NMR, HRMS). 16 of the newly synthesized compounds were analyzed by single-crystal X-ray crystallography confirming the spectral data and providing new structural information at the molecular and state-state levels, especially spectroscopically and catalytically relevant aggregation.

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