UV-vis, MCD, and computational studies of the electronic structures of core-modified porphyrins and phthalocyanines
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The electronic structures and optical properties of a large variety of core-modified porphyrins, phthalocyanines (Pcs), naphthalocyanines (Ncs), and anthracocyanines (Acs) were investigated using UV-vis and magnetic circular dichroism (MCD) methods. In some cases, electrochemistry and spectroelectrochemistry were used to further probe the electronic structures of these compounds. In addition, Density Functional Theory (DFT), and Time Dependent DFT (TDDFT) approaches were also employed to correlate experimental properties with the electronic structures of the target compounds. Several types of ligands (bulky, electronwithdrawing, and electron-donating) were incorporated onto the respective macrocyclic peripheries to determine trends and the best macrocycle-substituent combination for its suitable application. The most prominent applications of the molecules studied in this thesis are photochemotherapeutics for photodynamic cancer therapy (PDT), light-harvesting, and optical materials. Speaking directly to their PDT and near infra-red (NIR) solar cell applications, the compounds that had the strongest and furthest red-shifted absorptions in the NIR region of the optical absorption spectrum were macrocycles with greatly extended π-systems (the Ncs and Acs) which also featured bulky, electron-donating ligands.