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Electrostatic vs. electronic interactions within oxidized multinuclear Pt(bipyridine)(dithiolene) complexes
Khalil Youssef1, Antoine Vacher1, Thanaphon Khrueawatthanawet1
1Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) - UMR 6226, F-35000 Rennes, France. dominique.lorcy@univ-rennes1.fr.
Synthesized platinum complexes show unique electronic behavior. Spectroelectrochemistry reveals distinct near-infrared absorption upon oxidation, influenced by linker position and electrolyte choice, indicating charge delocalization.
Area of Science:
- Inorganic Chemistry
- Electrochemistry
- Materials Science
Background:
- Multinuclear platinum complexes with bipyridine and dithiolene ligands are key for studying electron transfer.
- Understanding redox behavior in such systems is crucial for developing novel electronic materials.
Purpose of the Study:
- To synthesize and characterize novel bi- and trimetallic platinum(bipyridine)(dithiolene) complexes.
- To investigate the influence of organic linkers and supporting electrolytes on the redox properties and electronic transitions of these complexes.
Main Methods:
- Synthesis of multinuclear platinum complexes.
- Electrochemical studies including cyclic voltammetry.
- Spectroelectrochemical analysis in dichloromethane.
Main Results:
- Complexes exhibited a single oxidation process with a standard electrolyte ([NBu4][PF6]).
- Spectroelectrochemistry revealed position-dependent near-infrared (NIR) absorption upon oxidation for specific isomers.
- Sequential oxidation and varying redox potentials were observed with a non-coordinating electrolyte ([Na][B(C6H4(CF3)2)4]), indicating charge delocalization and electrostatic effects.
Conclusions:
- The electronic communication and redox behavior of platinum complexes are highly sensitive to linker geometry and electrolyte properties.
- The observed NIR absorption suggests significant charge delocalization in mixed-valent intermediates, crucial for electronic applications.
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