Mössbauer and ESR Spectroscopic Studies on the Mixed-Valence States of 1′,1'″-Dialkyl- and 1′,1'″-Bis(methylbenzyl)biferrocenium Triiodides in Crystalline and Dispersed State
- 1 May 1987
- journal article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 60 (5) , 1673-1680
- https://doi.org/10.1246/bcsj.60.1673
Abstract
Iron atoms in the two different crystal forms of 1′,1'″-dibutylbiferrocenium triiodide showed different temperature-depending mixed-valence states; i.e., an averaged-valence state at higher temperatures and a trapped-valence state at lower temperatures in one crystal form but only a trapped-valence state from 78 K to room temperature in the other crystal form. The temperature-depending mixed-valence states were observed in 1′,1'″-diisobutylbiferrocenium triiodide, whereas only a trapped-valence state was found in 1′,1'″-dipentylbiferrocenium triiodide. Both the 1′,1'″-dibutyl- and 1′,1'″-diisobutylbiferrocenium triiodide showed Mössbauer spectra that were different from those of their crystalline states in a dispersed state. A good correlation of the anisotropy of g-values with the mixed-valence states was observed in the ESR spectra for a series of 1′,1'″-dialkyl- and 1′,1'″-bis(methylbenzyl)biferrocenium triiodides. The difference in the ESR parameters between these compounds in the crystalline state was reduced in the dispersed state.Keywords
This publication has 9 references indexed in Scilit:
- Mixed-valence 1',6'-dihalobiferrocenium cations: counterions micromodulating intramolecular electron transferJournal of the American Chemical Society, 1986
- Mössbauer Spectroscopic Study on the Mixed-Valence States of 1′,1'″-Bis(o-methylbenzyl)-, 1′,1'″-Bis(m-methylbenzyl)-, and 1′,1'″-Bis(p-methylbenzyl)biferrocenium TriiodideBulletin of the Chemical Society of Japan, 1986
- Studies on the Valence State of Iron Atoms in the Mixed-Valence Binuclear Ferrocenes by X-Ray Absorption Near Edge Structure (XANES) and by X-Ray Photoelectron Spectroscopy (XPS)Bulletin of the Chemical Society of Japan, 1986
- Counterion effects on the intramolecular electron-transfer rate of mixed-valence biferrocenium salts: micromodulation and phase transitionsJournal of the American Chemical Society, 1986
- Mixed-valence 1',6'-dihalobiferrocenium salts: the effects of the solid-state environment on electron-transfer ratesJournal of the American Chemical Society, 1986
- Mixed-valence dialkylbiferrocenium salts: an explanation for the observed temperature dependence of electron-transfer ratesJournal of the American Chemical Society, 1985
- The Temperature Dependence of the Trapped and Averaged-valence State in Mono-oxidized DialkylbiferrocenesBulletin of the Chemical Society of Japan, 1981
- Electron transfer in mixed-valent diferrocenylacetylene and [2.2]ferrocenophane-1,13-diyneInorganic Chemistry, 1980
- Electron transfer in oxidized biferrocene, biferrocenylene, and [1.1]ferrocenophane systemsInorganic Chemistry, 1975