Design, synthesis, and structural study of porphyrin-based organic materials
MetadataShow full item record
The unique properties of porphyrins, such as intense light absorption and emission, electron and oxygen transporting ability, make porphyrins desirable targets to incorporate into conjugated polymers for potential applications as semiconductors, or optic-electronic devices. However, low solubility and the lack of efficient polymerization methods have hampered the exploitation of monomeric porphyrins. The focus of this research is design and synthesis of highly soluble porphyrin monomers, and investigation of polymerization methods for constructing highly conjugated, high quality porphyrin materials. The accomplishments in this work include (1) study of solubility-structure relationships in porphyrins; (2) structure design to increase porphyrin solubility in organic solvents; (3) synthesis of a group of novel porphyrin molecules with specific structure design; (4) structure analysis of soluble porphyrin molecules by X-ray crystallography; (5) synthesis of monomers for porphyrin polymerization; (6) development and comparison of polymerization methods, including palladium mediated oxidative coupling, acyclic diyne metathesis (ADIMET) and acyclic diene metathesis (ADMET). Porphyrin solubility has been increased by tens to thousands of times when compared to other alkylporphyrins in this work. Alkene and alkyne metatheses reactions, which are applied for the first time to porphyrin polymerizations, show promising results for the preparation of defect-free conjugated porphyrin polymers.