Interplay of Charge Transfer, Dimensionality, and Amide Hydrogen Bond Network Adaptability in TCNQF4 Complexes of EDO-TTF-CONH2 and EDT-TTF-CONH2
✍ Scribed by Stéphane A. Baudron; Cécile Mézière; Karine Heuzé; Marc Fourmigué; Patrick Batail; Philippe Molinié; Pascale Auban-Senzier
- Publisher
- Elsevier Science
- Year
- 2002
- Tongue
- English
- Weight
- 278 KB
- Volume
- 168
- Category
- Article
- ISSN
- 0022-4596
No coin nor oath required. For personal study only.
✦ Synopsis
EDO-TTF-CONH 2 ][TCNQF 4 ], triclinic system, space group P-1, a ¼ 8:2479ð12Þ ( A, b ¼ 12:282ð2Þ ( A, c ¼ 12:6842ð18Þ ( A, a ¼ 113:850ð17Þ1, b ¼ 106:420ð17Þ1, c ¼ 90:284ð19Þ1, V ¼ 1116:8ð4Þ ( A 3 ; and [EDT-TTF-CONH 2 ] 2 [TCNQF 4 ], triclinic system, space group P-1, a ¼ 6:5858ð9Þ ( A, b ¼ 11:699ð2Þ ( A, c ¼ 12:2281ð18Þ
, whose p-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 p-acceptor. ½EDO-TTF-CONH dþ 2 2 ½TCNQF dÀ 4 2 is a diamagnetic insulating ionic salt with a threedimensional rock-salt-type structure based on discrete dimers while in the semi-conducting mixed-valence complex, ½EDT-TTF-CONH 2 dþ 2 ½TCNQF dÀ 4 ; 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. # 2002 Elsevier Science (USA)