Tetra S-confused porphyrinoids.

Area of Science:

• * Organic Chemistry
• * Supramolecular Chemistry
• * Materials Science

Background:

• * Porphyrinoids are macrocyclic compounds with diverse applications.
• * Achieving 'confusion' in porphyrinoids, through altered connectivity, is a key synthetic challenge.
• * Understanding structure-property relationships in these complex systems is crucial.

Purpose of the Study:

• * To synthesize and characterize novel 'confused' porphyrinoid macrocycles.
• * To investigate the impact of 2,4-connectivity on structural, electronic, and redox properties.
• * To compare these novel systems with parent porphyrinoids.

Main Methods:

• * Single crystal X-ray diffraction for structural determination.
• * Quantum chemical calculations to elucidate electronic features and aromaticity.
• * Spectroscopic and electrochemical methods for property analysis.

Main Results:

• * Synthesis of 20π confused porphyrazines and 30π expanded porphyrazines.
• * Unique cross-conjugated structures arising from 2,4-heterocycle linkage.
• * Significant differences in electronic and redox properties compared to parent porphyrazines.
• * Experimental and computational validation of structural and aromatic characteristics.

Conclusions:

• * 2,4-connectivity in heterocycles is an effective strategy for creating highly 'confused' porphyrinoids.
• * These novel macrocycles exhibit distinct properties due to cross-conjugation.
• * The findings provide fundamental insights into the chemistry of complex porphyrinoid systems.