Interplay of Charge Transfer, Dimensionality, and Amide Hydrogen Bond Network Adaptability in TCNQF4 Complexes of EDO-TTF-CONH2 and EDT-TTF-CONH2 Article - Novembre 2002

Stephane Baudron, Cécile Mézière, Karine Heuzé, Marc Fourmigué, Patrick Batail, Philippe Molinié, Pascale Auban-Senzier

Stephane Baudron, Cécile Mézière, Karine Heuzé, Marc Fourmigué, Patrick Batail, Philippe Molinié, Pascale Auban-Senzier, « 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, novembre 2002, pp. 668-674. ISSN 0022-4596

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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