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Linear 6,6'-biazulenyl framework featuring isocyanide termini: synthesis, structure, redox behavior, complexation,
Tiffany R Maher1, Andrew D Spaeth, Brad M Neal
1Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, Kansas 66045, USA.
Researchers synthesized the first nonbenzenoid diisocyanobiaryl via an unexpected homocoupling reaction. This novel compound exhibits reversible electrochemical reduction and unique surface adsorption properties on gold surfaces.
Area of Science:
- Organic Chemistry
- Materials Science
- Electrochemistry
Background:
- Nonbenzenoid aromatic compounds offer unique electronic properties.
- Diisocyanobiaryl structures are of interest for coordination chemistry and materials science.
- Azulene derivatives present distinct electronic and structural characteristics.
Purpose of the Study:
- To synthesize and characterize the first nonbenzenoid diisocyanobiaryl (species 5).
- To investigate the electrochemical properties of species 5.
- To explore the surface adsorption behavior of species 5 on gold surfaces.
Main Methods:
- Unexpected homocoupling of a 6-bromoazulene derivative.
- Electrochemical analysis (cyclic voltammetry).
- Computational studies (density functional theory).
- Surface adsorption studies on Au(111).
Main Results:
- Successful synthesis of the novel nonbenzenoid diisocyanobiaryl (species 5).
- Demonstrated reversible 2e(-) reduction of species 5.
- Observed correlation between substituent effects and electronic transitions in related biazulenyl derivatives.
- Species 5 forms end-on (η(1)) self-assembled monolayers on Au(111).
- Facile bimetallic coordination via the isocyano (-NC) termini.
Conclusions:
- The study presents a novel synthetic route to nonbenzenoid diisocyanobiaryls.
- Species 5 exhibits interesting electrochemical and surface-binding capabilities.
- The findings open avenues for designing new functional materials based on azulene scaffolds.
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