Heptatriene-Fused B^III Subporphyrins

Area of Science:

• Organic Chemistry
• Supramolecular Chemistry
• Materials Science

Background:

• Subporphyrins are macrocyclic compounds with unique electronic and photophysical properties.
• Fused porphyrinoids offer opportunities for tuning molecular characteristics.
• The synthesis of complex fused macrocycles remains a challenge in organic chemistry.

Purpose of the Study:

• To synthesize novel cycloheptatriene-fused B^III subporphyrins.
• To explore the synthesis of naphthalene- and benzocycloheptatriene-fused B^III subporphyrins.
• To investigate the impact of fused ring systems on the properties of B^III subporphyrins.

Main Methods:

• Wittig methoxymethylenation and acid-catalyzed cyclization for singly and doubly fused subporphyrins.
• Intramolecular McMurry coupling followed by oxidative annulation for naphthalene- and benzocycloheptatriene-fused subporphyrins.
• Characterization of synthesized compounds using spectroscopic and electrochemical techniques.

Main Results:

• Successful synthesis of singly and doubly cycloheptatriene-fused B^III subporphyrins (3 and 6).
• Obtained naphthalene- and benzocycloheptatriene-fused B^III subporphyrin (9) along with side products (10 and 11).
• Demonstrated that B^III subporphyrin 9 exhibits altered optical and electrochemical properties compared to parent subporphyrins.

Conclusions:

• Developed synthetic routes for novel fused B^III subporphyrins.
• The fused ring systems significantly influence the photophysical and electrochemical behavior of B^III subporphyrins.
• These findings contribute to the development of new functional macrocyclic materials.