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Interplay of Charge Transfer, Dimensionality, and Amide Hydrogen Bond Network Adaptability in TCNQF4 Complexes of EDO-TTF-CONH2 and EDT-TTF-CONH2

Abstract : [EDO-TTF-CONH2][TCNQF4], triclinic system, space group P-1, a=8.2479(12) Å, b=12.282(2) Å, c=12.6842(18) Å, α=113.850(17)°, β=106.420(17)°, γ=90.284(19)°, V=1116.8(4) Å3; and [EDT-TTF-CONH2]2[TCNQF4], triclinic system, space group P-1, a=6.5858(9) Å, b=11.699(2) Å, c=12.2281(18) Å, α=104.000(19)°, β=93.611(17)°, γ=98.279(19)°, V=899.9(3) Å3, whose π-donor molecules, (ethylenedioxo)-carbamoyltetrathiafulvalene and (ethylenedithio)-carbamoyltetrathiafulvalene, respectively, differ solely by the nature of the chalcogen atoms in their outer ethylene dichalcogeno bridge, yet form very different charge-transfer complexes with the same π-acceptor. [EDO-TTF-CONH2•+]2 [TCNQF4•−]2 is a diamagnetic insulating ionic salt with a three-dimensional rock-salt-type structure based on discrete dimers while in the semi-conducting mixed-valence complex, [EDT-TTF-CONH2]2•+[TCNQF4•−], the mixed-valence dimers aggregate into infinite chains interspersed within parallel rows of non-interacting radical anions. It is shown how the robust and adaptable supramolecular amide hydrogen bond tweezers-like motifs common to the two solids simply comply to the 3-to-1 dimensionality reduction upon substitution of O for S.
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https://hal.univ-angers.fr/hal-02545418
Contributeur : Cécile Meziere <>
Soumis le : vendredi 17 avril 2020 - 09:44:41
Dernière modification le : mercredi 16 septembre 2020 - 16:40:15

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Stephane Baudron, Cécile Mézière, Karine Heuzé, Marc Fourmigué, Patrick Batail, et al.. Interplay of Charge Transfer, Dimensionality, and Amide Hydrogen Bond Network Adaptability in TCNQF4 Complexes of EDO-TTF-CONH2 and EDT-TTF-CONH2. Journal of Solid State Chemistry, Elsevier, 2002, 168 (2), pp.668-674. ⟨10.1006/jssc.2002.9765⟩. ⟨hal-02545418⟩

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