Synthesis and structural characterization of a nonaromatic dithia-di-2,6-naphthioctaphyrin(1.0.0.1.1.0.0.1)

Area of Science:

• Organic Chemistry
• Supramolecular Chemistry
• Materials Science

Background:

• Expanded porphyrins are macrocyclic compounds with unique photophysical and electronic properties.
• Incorporating aromatic units like naphthalene can modulate the properties of porphyrin frameworks.
• Understanding the structure-property relationships of novel macrocycles is crucial for developing new functional materials.

Purpose of the Study:

• To synthesize a novel expanded porphyrin incorporating naphthalene units.
• To characterize the synthesized macrocycle, dithia-di-2,6-naphthioctaphyrin(1.0.0.1.1.0.0.1).
• To investigate the aromaticity and solid-state conformation of the new macrocycle.

Main Methods:

• Straightforward synthetic route for macrocycle construction.
• Nuclear Magnetic Resonance (NMR) spectroscopy for structural elucidation.
• Single-crystal X-ray diffraction analysis for solid-state structure determination.
• Density Functional Theory (DFT) calculations for electronic structure analysis.

Main Results:

• Successful synthesis of dithia-di-2,6-naphthioctaphyrin(1.0.0.1.1.0.0.1) incorporating a naphthalene unit.
• NMR, X-ray diffraction, and DFT calculations confirmed the macrocycle is nonaromatic.
• Single-crystal X-ray analysis revealed a twisted conformation in the solid state.

Conclusions:

• A novel nonaromatic expanded porphyrin containing naphthalene units was synthesized.
• The synthesized macrocycle exhibits a twisted conformation, influencing its electronic properties.
• This study provides insights into the synthesis and structural characterization of complex porphyrin derivatives.