Modulation of redox potentials utilizing the flexible coordination sphere of a penta-coordinate complex in the solid
Ryo Ohtani1, Yuu Kitamura1, Yuh Hijikata2
1Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1, Kurokami, Chuo-ku, Kumamoto 860-8555, Japan. ohtani@sci.kumamoto-u.ac.jp hayami@sci.kumamoto-u.ac.jp.
Dalton Transactions (Cambridge, England : 2003)
|March 7, 2017
Summary
Structural changes in manganese(V)-nitrido complexes, achieved through a lipid package approach, significantly influence redox potentials. Smaller bond angles in the manganese complex correlate with higher redox potentials, offering insights into electron transfer mechanisms.
Area of Science:
- Inorganic Chemistry
- Electrochemistry
- Materials Science
Background:
- Manganese-nitrido complexes are of interest due to their unique electronic structures.
- Understanding redox potentials is crucial for designing new functional materials.
- The "lipid package" approach offers a novel method for modifying coordination complex properties.
Purpose of the Study:
- To investigate the impact of subtle structural modifications on the redox potentials of manganese(V)-nitrido anionic complexes.
- To explore the relationship between coordination geometry and electrochemical behavior.
- To synthesize and characterize novel manganese-nitrido complexes within lipid assemblies.
Main Methods:
- Synthesis of single crystals of four lipid assemblies containing the manganese(V)-nitrido complex.
- Solid-state cyclic voltammetric studies to determine redox potentials.
- Density Functional Theory (DFT) calculations to support experimental findings.
Main Results:
- A clear correlation was observed between the "cross" NC-Mn-CN bond angles and the redox potentials of the complexes.
- Smaller bond angles were associated with higher redox potentials.
- DFT calculations corroborated the experimental trend, explaining the energy changes during redox transitions.
Conclusions:
- Subtle changes in the coordination structure of manganese(V)-nitrido complexes significantly tune their redox potentials.
- The NC-Mn-CN bond angle serves as a reliable predictor of redox potential in the solid state.
- This study demonstrates the utility of the "lipid package" approach for fine-tuning the electrochemical properties of inorganic complexes.
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