Chiral Bis(tetrathiafulvalene)-1,2-cyclohexane-diamides

Area of Science:

• Organic Chemistry
• Materials Science
• Supramolecular Chemistry

Background:

• Chiral organic molecules are crucial for asymmetric synthesis and advanced materials.
• Tetrathiafulvalene (TTF) derivatives are known for their unique electronic properties.
• Developing new chiral TTF-based compounds with tunable properties is an active research area.

Purpose of the Study:

• To synthesize novel chiral bis(TTF) diamides.
• To characterize their structural, chiroptical, and electronic properties.
• To explore their potential as semiconductor materials.

Main Methods:

• Synthesis of chiral bis(TTF) diamides from 1,2-cyclohexane-diamine and TTF acyl chlorides.
• Characterization using circular dichroism (CD) and single-crystal X-ray diffraction.
• Electrochemical studies including chemical oxidation and electrocrystallization.
• Single-crystal resistivity measurements and DFT/TD-DFT calculations.

Main Results:

• Chiral bis(TTF) diamides were obtained in good yields (54-74%).
• The racemic form displayed a pincer-like framework stabilized by intramolecular S···S interactions.
• Stable oxidized species and radical cation salts were formed upon oxidation.
• Resistivity measurements revealed semiconductor behavior in the racemic donor with AsF6- counterions.

Conclusions:

• The successful synthesis and characterization of new chiral bis(TTF) diamides.
• Demonstration of semiconductor properties in these novel TTF derivatives.
• Validation of structural and chiroptical features through computational studies.
• Potential for these chiral TTF donors in the development of advanced electronic materials.