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Porphyrazinehexamines and Dinitroporphyrazines: Synthesis, Characterization, and Complementary Electrochemistry.
Hanlin Nie1, Anthony G. M. Barrett, Brian M. Hoffman
1Department of Chemistry, Northwestern University, Evanston, Illinois 60208, and Department of Chemistry, Imperial College of Science, Technology and Medicine, London SW7 2AY, U.K.
The Journal of Organic Chemistry
|October 25, 2001
Summary
Unsymmetrical porphyrazines were synthesized using readily available materials. These novel compounds, including dinitroporphyrazines, exhibit unique electrochemical properties, showing easier oxidation and distinct reduction potentials.
Area of Science:
- Organic Chemistry
- Macromolecular Chemistry
- Electrochemistry
Background:
- Porphyrazines are macrocyclic compounds with diverse applications.
- Unsymmetrical porphyrazines offer tunable electronic and optical properties.
- Efficient synthesis of unsymmetrical porphyrazines remains a challenge.
Purpose of the Study:
- To synthesize novel unsymmetrical porphyrazines with varying peripheral substituents.
- To investigate the electrochemical behavior of these synthesized compounds.
- To explore the nitration of free-base and nickel porphyrazines.
Main Methods:
- Linstead crossover macrocyclization reactions.
- Demetalation using trifluoroacetic acid (TFA).
- Nitration using nitrogen dioxide.
- Electrochemical studies (cyclic voltammetry).
Main Results:
- Successful synthesis of unsymmetrical porphyrazines (2, 4, 6) and their nickel complex (7).
- Pyrrolines 11 and 12 proved to be superior co-cyclization partners.
- Nitration yielded dinitroporphyrazines (18, 19).
- Electrochemical studies revealed porphyrazinehexamine 2 is easily oxidized; dinitroporphyrazine 18 showed cathodic shifts in reduction waves.
Conclusions:
- Unsymmetrical porphyrazines can be efficiently synthesized from accessible precursors.
- Peripheral substitution significantly influences the electrochemical properties.
- The developed synthetic routes provide access to functionalized porphyrazines for further studies.