Electron-transfer rates by dielectric relaxometry and the direct-current conductivities of solid homonuclear and heteronuclear mixed-valence metal cyanometallates and of the Methylene Blue–iron dithiolate adduct
- 1 January 1987
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
- Vol. 83 (2) , 245-255
- https://doi.org/10.1039/f19878300245
Abstract
Dielectric relaxation (DR) frequencies for electron transfer in a series of metal hexacyanometallates have been compared with values from d.c. conductivity. If the compounds do not show evidence of proton conduction, the agreement is good, so establishing a site-transfer electronic conduction mechanism. Cu2Fe(CN)6 shows some disagreement, while marked anomalies with CoII 3[CoIII(CN)6] and FeII 3[CrIII(CN)6]2 are ascribed to proton conduction and electrode processes. Despite variation from sample to sample in the Methylene Blue–dithiolate adduct, the relaxation/conductivity relationships for each is also satisfactory for this single-metal-ion complex, bis[3,7-bis(dimethylaminophenazathionium)] tris(maleonitriledithiolato) iron2–.Keywords
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