Abstract:
This thesis investigates the synthesis, characterization, and redox properties of "Tetra S-Confused Porphyrinoids" and "Porphyrinoids with Thiophenes and Phenanthroline." The research explores both confused and expanded porphyrinoids, with a focus on understanding the influence of aromaticity and structural modification on their electronic and redox behaviors. Central to the study are porphycenes, structural isomers of porphyrins, and novel macrocyclic architectures incorporating heterocyclic units such as thiophene and phenanthroline. A key aim is to explore how these modifications affect the redox properties and metal coordination abilities of the porphyrinoids, creating opportunities for applications in catalysis, materials science, and molecular electronics. Synthesized compounds are characterized using spectroscopic methods (UV-Vis, NMR) and solid-state analyses (single-crystal X-ray diffraction). Redox properties are evaluated through cyclic voltammetry and variable-temperature electron paramagnetic resonance (VT-EPR), supported by quantum mechanical calculations. The work introduces novel confused porphycenes and expanded macrocycles, such as tetrathia porphycenes and phenanthroline-embedded isoamethyrins. The synthesis of these compounds highlights unique structural and electronic properties, such as the formation of organometallic complexes, stabilization of organic radicals, and potential use as molecular sponges. By combining macrocyclic frameworks with metal-coordinating ligands, this thesis expands the understanding of these systems, paving the way for their use in molecular sensing, asymmetric catalysis, and supramolecular chemistry.
