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Redox-induced solid-solid state transformation of tetrathiafulvalene (TTF) microcrystals into mixed-valence and π-dimers in the presence of nitrate anions

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Abstract

Tetrathiafulvalene (TTF), when dissolved in an organic solvent, can be electrochemically oxidized to the cation radical TTF+• and the dication TTF2+. In aqueous Co(NO3)2 electrolyte media, TTF chemically modified electrodes undergo a very different TTF to TTF+•pathway to give two solid-solid state conversion reactions. Initially, the mixed-valent (TTF)2NO3, containing (TTF-TTF+•) as a dimeric cation, is formed, which in turn can be oxidized to (TTF)2(NO3)2, containing the (TTF+•)2 dimeric cation. These processes occur by nucleation-growth mechanisms on glassy carbon, platinum, gold and indium-tin oxide electrode substrates containing adhered TTF solid. The products have been characterized by spectroscopic and voltammetric methods and (TTF)2(NO3)2 also has been synthesized by reaction of TTF+•, prepared by bulk electrolysis in acetonitrile with (Bu4N)NO3, using the appropriate stoichiometric molar ratios.

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Authors and Affiliations

  1. School of Chemistry, Monash University, Clayton, VIC, 3800, Australia

    Shaimaa M. Adeel, Lisandra L. Martin & Alan M. Bond

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  1. Shaimaa M. Adeel
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  2. Lisandra L. Martin
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  3. Alan M. Bond
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Correspondence to Lisandra L. Martin or Alan M. Bond.

Additional information

A contribution to the celebration of the 65th birthday of our colleague and friend, Stephen Fletcher.

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Adeel, S.M., Martin, L.L. & Bond, A.M. Redox-induced solid-solid state transformation of tetrathiafulvalene (TTF) microcrystals into mixed-valence and π-dimers in the presence of nitrate anions. J Solid State Electrochem 18, 3287–3298 (2014). https://doi.org/10.1007/s10008-014-2656-z

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  • DOI: https://doi.org/10.1007/s10008-014-2656-z

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