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Modular One-Pot Access to π-Expanded Tetrakis(Phenothiazinyl)-Silanes With Broadly Tunable Redox and Emission
Thomas P M Merke1, Lysander Presser1, Leonard Karl2
1Institut für Organische Chemie und Makromolekulare Chemie, Heinrich-Heine-Universität Düsseldorf, Düsseldorf, Germany.
Researchers developed new organic materials called tetrakis(phenothiazinyl)silanes with tunable electronic and light-emitting properties. This versatile scaffold allows independent control over redox and photophysical characteristics for advanced material applications.
Area of Science:
- Organic Materials Chemistry
- Supramolecular Chemistry
- Photophysics
Background:
- Developing multichromophoric materials with independently tunable redox and emissive properties is a significant challenge.
- Organic materials chemistry seeks advanced functional molecules for diverse applications.
Purpose of the Study:
- To synthesize and characterize a library of tetrakis(phenothiazinyl)silanes.
- To investigate the independent tunability of redox and emissive properties in these materials.
Main Methods:
- Modular one-pot BLEBS (bromine-lithium exchange-borylation-Suzuki) strategy for synthesis.
- Cyclic voltammetry for redox potential determination.
- Spectroscopic measurements (steady-state and time-resolved) for photophysical characterization.
- (TD-)DFT calculations for theoretical insights.
Main Results:
- A library of 21 tetrakis(phenothiazinyl)silanes was synthesized with varying substitution patterns and linker architectures.
- Redox potentials were tunable (+0.17 to +0.42 V vs Fc/Fc+) and predictable via Hammett correlations.
- Bright fluorescence (quantum yields up to 0.90) was observed, tunable from blue to yellow-green (441-533 nm) through linker engineering.
- 7-substitution modulated redox potentials, while linker modification controlled emission energy.
Conclusions:
- The tetrakis(phenothiazinyl)silane scaffold offers a versatile platform for independent control of electrochemical and photophysical properties.
- Systematic tuning of redox and emissive characteristics is achievable through targeted molecular design.
- These materials hold promise for applications requiring precisely controlled optoelectronic functionalities.
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