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Directly linked porphyrin arrays.
Naoki Aratani1, Atsuhiro Osuka
1Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan.
Chemical Record (New York, N.Y.)
|November 5, 2003
Summary
Researchers discovered a silver-promoted reaction to create linked porphyrin arrays. This method produced the longest discrete molecule (a 128-mer) and the most conjugated porphyrin tape to date.
Area of Science:
- Supramolecular Chemistry
- Materials Science
- Organic Synthesis
Background:
- Photosynthetic reaction centers utilize complex porphyrin structures.
- Synthesizing extended porphyrin arrays is challenging.
- Existing methods lack regioselectivity and scalability.
Purpose of the Study:
- To develop a novel method for synthesizing directly linked and fused porphyrin arrays.
- To explore the potential of these arrays in creating extended molecular architectures.
- To investigate the electronic properties of highly conjugated porphyrin systems.
Main Methods:
- Serendipitous discovery of Ag(I)-promoted oxidative meso-meso coupling of 5,15-diaryl Zn(II)-porphyrins.
- Synthesis of diverse porphyrin arrays: linear, windmill, grid, singly/doubly/triply linked, and fused structures.
- Oxidation of end-phenyl capped meso-meso-linked zinc porphyrins using DDQ-Sc(OTf)(3) to form porphyrin tapes.
Main Results:
- Successful synthesis of various porphyrin arrays with high regioselectivity.
- Creation of a discrete meso-meso-linked 128-mer, the longest man-made discrete molecule.
- Fabrication of a 12-mer porphyrin tape, the most extensively conjugated porphyrin array, with a low electronic band peak at 3500 cm(-1).
Conclusions:
- The Ag(I)-promoted meso-meso coupling is a versatile and efficient method for porphyrin array synthesis.
- This reaction enables the construction of unprecedentedly large and complex porphyrin architectures.
- The synthesized porphyrin tapes exhibit remarkable electronic conjugation, opening avenues for advanced materials.