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Expanded Indacene-Tetrathiafulvalene Scaffolds: Structural Implications for Redox Properties and Association Behavior
Johannes Fabritius Petersen1,2, Conerd K Frederickson2, Jonathan L Marshall2
1Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|July 12, 2017
Summary
Researchers synthesized novel indacene-tetrathiafulvalene (TTF) hybrids. Molecular design controls redox properties and prevents unwanted dimerization, enabling new reversible assemblies.
Area of Science:
- Organic Chemistry
- Materials Science
- Supramolecular Chemistry
Background:
- Redox-controlled dimerization of tetrathiafulvalene (TTF) derivatives is crucial for creating reversible molecular assemblies.
- Understanding the relationship between molecular structure and self-assembly behavior is key in materials design.
Purpose of the Study:
- To synthesize and characterize novel indacene-TTF hybrids with varying fused units (naphtho, benzothieno).
- To investigate how the orientation of fused units and bulky substituents influence redox properties and dimerization.
- To establish a general synthetic method for superextended TTFs.
Main Methods:
- Synthesis of indacene-TTF hybrids via Horner-Wadsworth-Emmons reactions.
- Characterization of synthesized compounds using spectroscopic and electrochemical techniques.
- Analysis of structure-property relationships concerning redox behavior and π-dimer formation.
Main Results:
- The orientation of fused naphtho or benzothieno units significantly impacts redox properties and the propensity for dimerization.
- Geometrical constraints leading to nonplanar π-systems effectively suppress mixed-valence and π-dimer complex formation.
- Bulky substituents, such as (triisopropylsilyl)ethynyl groups on indenofluorene and diindenoanthracene scaffolds, also prevent association.
- Horner-Wadsworth-Emmons reactions provide a versatile route to superextended TTFs using polycyclic conjugated hydrocarbon diones.
Conclusions:
- Molecular design, including the choice of fused units and substituents, offers precise control over the redox-driven self-assembly of TTF derivatives.
- Suppression of dimerization through nonplanar structures or bulky groups is a viable strategy for achieving stable, non-associated oxidized states.
- The developed synthetic methodology enables access to a broader range of complex, superextended TTF systems for advanced applications.
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