Issue 5, 2006

Current trends and future challenges in the experimental, theoretical and computational analysis of intervalence charge transfer (IVCT) transitions

Abstract

Mixed-valence chemistry has a long and rich history which is characterised by a strong interplay of experimental, theoretical and computational studies. The intervalence charge transfer (IVCT) transitions generated in dinuclear mixed-valence species (particularly of ruthenium and osmium) have received considerable attention in this context, as they provide a powerful and sensitive probe of the factors which govern electronic delocalisation and the activation barrier to intramolecular electron transfer. This tutorial review discusses classical, semi-classical and quantum mechanical theoretical treatments which have been developed over the past 35 years for the analysis of IVCT absorption bands. Particular attention is drawn to the applicability of these models for the analysis of mixed-valence complexes which lie between the fully localised (Class II) and delocalised (Class III) limits in the “localised-to-delocalised” (Class II–III) regime. A clear understanding of the complex interplay of inter- and intramolecular factors which influence the IVCT process is crucial for the design of experimental studies to probe the localised-to-delocalised regime and in guidance of the development of appropriate theoretical models.

Graphical abstract: Current trends and future challenges in the experimental, theoretical and computational analysis of intervalence charge transfer (IVCT) transitions

Article information

Article type
Tutorial Review
Submitted
06 Janv. 2006
First published
08 Febr. 2006

Chem. Soc. Rev., 2006,35, 424-440

Current trends and future challenges in the experimental, theoretical and computational analysis of intervalence charge transfer (IVCT) transitions

D. M. D'Alessandro and F. R. Keene, Chem. Soc. Rev., 2006, 35, 424 DOI: 10.1039/B514590M

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