Synthesis of porphyrins and expanded porphyrins from oligopyrrolic compounds and investigation of their photophysical properties

Porphyrin compounds are important structures found in biological systems where magnesium-porphyrin transfers electrons in photosynthesis and iron-porphyrin is responsible from oxygen transport. In the last decades, porphyrins have found applications as photosensitizing organic molecules in the fields of cancer researches, electron transfer systems or dye sensitized solar cell studies. Selective synthesis of porphyrins having functional groups with high yields is important. In this work, selective syntheses of A4B2-hexaphyrins from Lewis acid catalyzed addition reactions of meso-aryl substituted oligopyrroles and aryl substituted N-tosylimines has been studied and the photophysical properties of the obtained macrocyclic structures were investigated. With this purpose in the first part of the work, the synthesis of meso-aryl substituted tripyrrane and aryl substituted N-tosylimine compounds as the starting materials were carried out. A4B2-hexaphyrin compounds were obtained from the addition and cyclization reactions of the starting materials. Effects of substituent on the aryl groups of starting materials on the formation of A4B2-hexaphyrin compounds were investigated. In these reactions, substituent dependent formation of A3B-porphyrins as side products along with A4B2-hexaphyrins or as main product was shown. Formation mechanism of A4B2-hexaphyrins A3B-porphyrins was studied by mass spectroscopy in timely manner. In the last part of the work, diad systems having BODIPY and porphyrin units were synthesized which are able to transfer energy within the molecule. In these systems, effects of aryl substituents and the distance between the chromophores on energy transfer is searched. Photoinduced intramolecular energy transfer of the diad molecules was shown according to the spectroscopic analysis studies. Structures of the synthesized molecules during this thesis were identified by 1H NMR, 13C NMR, 19F NMR, UV-visible, Flourescent Spectroscopy and HR MS techniques.