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DOI: 10.1039/A902690H (Paper) Reference Section for: J. Mater. Chem., 1999, 9, 2359-2363

New radical salts of diferrocenyl-VT (VT: bis(vinylenedithio)tetrathiafulvalene)

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Ha-Jin Lee, Dong-Youn Noh, Allan E. Underhill and Choong-Sub Lee

Abstract

1,1′-Diferrocenyl-VT 5 is successfully prepared by phosphite-based coupling reaction of ferrocenyl 1,3-dithiol-2-one 4. It shows one reversible cyclic voltammogram with Epa = 0.66 V and forms radical cation salts with I3– and BF4–. In compound 5·(I3), according to the temperature-controlled EPR and Mössbauer measurements, the VT moiety is oxidised to form a radical, while the two ferrocene groups are not oxidized. In compound 5H·(BF4)4, however, a mixed ferrocene/ferrocenium system consisting of low-spin Fe(II), high-spin Fe(II) and Fe(III) is detected by Mössbauer spectroscopy. Due to the protonation of VT by HBF4, the extended π-electron system of VT is degraded into the TTF system. The electrical conductivities of pressed pellets of the radical cationic salts are 7 × 10–3 S cm–1.

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