Conceptual Understanding of Mixed-Valence Compounds and Its Extension to General Stereoisomerism
- Publisher:
- WILEY-VCH
- Publication Type:
- Chapter
- Citation:
- Mixed-Valence Systems: Fundamentals, Synthesis, Electron Transfer, and Applications, 2023, pp. 45-91
- Issue Date:
- 2023-01-01
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| Filename | Description | Size | |||
|---|---|---|---|---|---|
| 21658625_12314192150005671.pdf | 2.35 MB |
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Isomerism in mixed-valence compounds is usually interpreted semi-quantitatively using the coupled harmonic oscillator model introduced by Hush. This review first considers the primary qualitative scenarios envisaged by his model: the weak-coupling regime in which non-adiabatic effects become critical, the intermediate-coupling regime typical of most chemical systems, the regime in which anharmonicity is critical, the strong-coupling regime typical of delocalized mixed-valence compounds, and the inverted regime in which reactions slow down with increasing exothermicity. In particular, different observable features, including, structural, spectroscopic, kinetic, Stark-effect, electrochemical, and spin resonance effects, are associated with each scenario. Extensions of the theory are then reviewed that facilitate applications to more general unimolecular isomerization processes. Treated uniformly, specific applications are then reviewed pertaining to traditional mixed-valence complexes including Prussian blue and the Creutz–Taube ion, primary charge separation during bacterial photosynthesis and in artificial devices, charge transport in molecular conductors, hydrogen bonding, the ammonia inversion reaction, identification of the primary feature causing the chemistry of first-row elements to differ so much from that of the later rows, and aromaticity.
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