Abstract
Abstract Intramolecular electron transfer in the mixed-valence biferrocenium complexes in crystals shows qualitatively different behavior from that in the complexes in solutions. The ‘extra’ electron in a mixed-valence complex in the crystal may be localized at low temperature and delocalized at higher temperature. The electron localization-delocalization transition induced thermally corresponds to a kind of order-disorder phase transition. In order to clarify the mechanism of the transition, a statistical mechanical model has been proposed (T. Kambara, D.N. Hendrickson, T.-Y. Dong, and M. J. Cohn, J. Chem. Phys., 86, 2362 (1987)). The temperature dependences of the physical quantities relevant to the cooperative electron localization-delocalization transition are calculated base on the model. In the calculation a more elaborate treatment is adopted for the intermolecular interactions. Those calculated values are compared with the observed ones for various kinds of mixed-valence biferrocenium trihalide cr...
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