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Magnetochemistry 2017, 3(1), 8; doi:10.3390/magnetochemistry3010008

New Ethylenedithio-TTF Containing a 2,2,5,5-Tetramethylpyrrolin-1-yloxyl Radical through a Vinylene Spacer and Its FeCl4− Salt—Synthesis, Physical Properties and Crystal Structure Analyses

Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Gakuen-cho, Naka-ku, Sakai 599-8531, Japan
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Received: 13 January 2017 / Accepted: 6 February 2017 / Published: 9 February 2017
(This article belongs to the Special Issue Magnetism of Molecular Conductors)
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Abstract

To develop novel magnetic conductors exhibiting conducting/magnetic bifunctionalities and peculiar responses to applied magnetic fields, we synthesized new EDT-TTF (ethylenedithiotetrathiafulvalene) donor containing a 2,2,5,5-tetramethylpyrrolin-1-yloxyl radical through a π-conjugated vinylene spacer 1 and examined its electronic and crystal structures, and physical properties. We also prepared its cation radical salts by an electrochemical oxidation method and successfully cleared the crystal structures and magnetic properties of the cation radical salts, 1·FeCl4 and 1·GaCl4. These salts have strongly dimerized one-dimensional arrays of the fully oxidized donor molecules, giving rise to the formation of spin-singlet state of the π cation radical spins in the dimer. On the other hand, the FeCl4- anion locates on the side of the dimers with very short S-Cl contacts and mediates very strong π-d interaction between the donor and anion moieties, resulting in the antiferromagnetic behavior of the Weiss temperature of θ = -3.9 K through its d-π-d interaction. View Full-Text
Keywords: TTF; molecular conductors; magnetic properties; X-ray crystal structure analyses; stable organic radicals; 2,2,5,5-tetramethylpyrrolin-1-yloxyl radical TTF; molecular conductors; magnetic properties; X-ray crystal structure analyses; stable organic radicals; 2,2,5,5-tetramethylpyrrolin-1-yloxyl radical
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Horikiri, K.; Fujiwara, H. New Ethylenedithio-TTF Containing a 2,2,5,5-Tetramethylpyrrolin-1-yloxyl Radical through a Vinylene Spacer and Its FeCl4− Salt—Synthesis, Physical Properties and Crystal Structure Analyses. Magnetochemistry 2017, 3, 8.

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