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Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Thiolated pi-extended tetrathiafulvalenes: versatile multifunctional pi-systems.
Christian A Christensen1, Andrei S Batsanov, Martin R Bryce
1Department of Chemistry, Durham University, Durham DH1 3LE, United Kingdom.
The Journal of Organic Chemistry
|January 26, 2007
Summary
New synthetic methods create novel ex-TTF derivatives with tunable redox properties. These compounds, featuring protected thiol groups, undergo deprotection and functionalization to form unique trimers, cyclophanes, and strained structures, offering insights into their electronic behavior and crystal packing.
Area of Science:
- Organic Chemistry
- Materials Science
- Electrochemistry
Background:
- 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (ex-TTF) derivatives are important in organic electronics.
- Developing efficient synthetic routes for novel ex-TTF structures is crucial for exploring their properties.
Purpose of the Study:
- To synthesize novel ex-TTF derivatives using a direct phosphite-mediated cross-coupling reaction.
- To investigate the redox properties and structural characteristics of these new compounds.
Main Methods:
- Direct phosphite-mediated cross-couplings of anthraquinone with 1,3-dithiole-2-thione derivatives.
- Deprotection of cyanoethyl-protected thiol groups and trapping with electrophiles.
- Cyclic voltammetry for redox property analysis.
- X-ray crystallography for structural determination.
Main Results:
- Successful synthesis of ex-TTF trimer 19, dimeric cyclophanes 22 and 25, tetrakis(hydroxyethylthio) derivative 23, and strained cyclophane 24.
- Compounds 19, 22, and 25 exhibit independent 2-electron redox behavior.
- Cyclophane 24 shows a positively shifted oxidation potential due to conformational constraints.
- X-ray structures reveal typical ex-TTF saddle-shape folding, enhanced in 24, and unique crystal packing in 23 solvates.
Conclusions:
- A novel and efficient synthetic methodology for ex-TTF derivatives has been established.
- The synthesized compounds display diverse redox behaviors and structural features.
- Structural modifications, such as bridging chains, significantly influence electronic properties.
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