Synthesis and crystal structure of a new unsymmetrical oxygen containing TTF
Source abstract
Abstract
Many chalcogen‐substituted derivatives of tetrathiafulvalene (TTF) are able to form metallic or even superconducting cation radical salts. The particular properties of bis(ethylenedithio)TTF (ET) prompted the synthesis of new oxygen‐containing analogues of ET. One such new molecule, ETOX, is presented, which, besides being a new π‐donor, is the first mono‐oxa derivative of ET. It is shown to be a promising donor for molecular metals and superconductors that gives cation radical salts with a variety of stoichiometries.
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Research context
OpenAlex topics: Organic and Molecular Conductors Research · Magnetism in coordination complexes · Solid-state spectroscopy and crystallography
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References (17)
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11. A 1:1 mixture of 6 and 7 was refluxed in freshly distilled P(OMe)3for 3 h. After cooling a dark precipitate was filtered off and washed with methanol. As judged by NMR and TLC this crude product mixture contained the unsymmetrical donor ETOX as the main product together with minor amounts of ET and traces of the other symmetrical derivative OXTTF. The mixture was chromatographed on silica eluting with CS2and ETOX 5 was obtained in 52% yield as an orange‐red solid. Data for 5:1H NMR: δ 3.20 (m 2H) 3.29 (s 4H) 4.45 (m 2H); 13C NMR: δ 26.8 31.0 68.5 91.6 109.8 111.3 114.3 114.6 136.3 The signal at 31.0 ppm was twice the intensity of the other methylene signals; MS 368 (M+ 29%) 340 (M+− C2H4 24%) 236 (78%) 208 (41%) 88 (100%).
12. In CH2Cl2at 298 K with Bu4NPF6as electrolyte vs SCE scan rate 100 m V/s.
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14. Crystal data for ETOX: C10H8OS7 Mr= 368.6 monoclinic space group P21/n a = 6.454(2) b = 14.036(3) c = 15.578(3) Å β = 93.02(4°) U = 1409.1(6) Å3 T = 293±1 K Z = 4. Dc= 1.737 g cm−3 λ = 0.71073 Å μ (Mo‐Ka) = 1.100 mm−1 analytical absorption correction; transmission range 0.6168–0.7107 (sinΘ/λ)max= 0.7056 Å−1 2171 reflections with I ≥0σ(I) 41 restraints and 175 parameters S = 1.0191 wR2 = 0.1671 R1 (I > 2s(I)) = 0.0565. Atoms C(8) C(9) and C(10) were disordered and refined in two positions each the site occupancies for the major conformation refined to 0.052(3) 0.59(2) and 0.54(1) respectively.
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