Highly Functionalized Tetrathiafulvalenes: Riding along the Synthetic Trail from Electrophilic Alkynes

Gorgues, A.; Hudhomme, Piétrick; Sallé, Marc

doi:10.1021/cr0306485

Cited by 164 publications

(55 citation statements)

References 336 publications

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“…The preparations are therefore limited to this specific derivative, together with the added inconvenience of the availability and handling of this gaseous alkyne. On the other hand, the 1,3-dipolar-addition reaction of activated acetylenes with ethylenetrithiocarbonate has proven to be one of the main routes in tetrathiafulvalene chemistry [34] since it affords, often in very good yield, 1,3-dithiole-2-thiones for further phosphate-or phosphine-coupling reactions to the TTF derivatives. For the introduction of only one CF 3 group on the dithiole ring, we therefore chose to start from the trifluoromethyl-substituted alkyne 6, where the presence of two electron-withdrawing groups, an ester and a trifluoromethyl group, should confer a good reactivity towards ethylenetrithiocarbonate, as was observed (see below).…”

Section: Resultsmentioning

confidence: 99%

Fluorine Segregation in Crystalline Materials: Structural Control and Solid‐State [2+2] Cycloaddition in CF₃‐Substituted Tetrathiafulvalene Derivatives

Jeannin

Fourmigué

2006

Chemistry A European J

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The well-known influence of long perfluorinated chains on the structures and stability of amphiphilic molecules in liquid crystalline mesophases or mesoscopic micellar arrangements is evaluated here in the realm of crystalline materials based on rigid aromatic molecules bearing only a limited number of CF(3) moieties. Tetrathiafulvalene (TTF) derivatives bearing one or two CF(3) groups, that is, (Z)- and (E)-(CF(3))(2)TTF ((Z)-1, (E)-1), EDT-TTF-CF(3) (2), and EDT-TTF(CF(3))(2) (3) (EDT=ethylenedithio) are prepared from the 1,3-dipolar reaction of methyl 4,4,4-trifluorotetrolate with ethylenetrithiocarbonate. The structures of neutral (Z)-1, (E)-1, 2, and 3 as indicated by single-crystal X-ray diffraction measurements reveal the recurrent formation of layered structures with a strong segregation of the fluorinated moieties and formation of fluorous bilayers, attributed to the amphiphilic character of those TTF derivatives upon CF(3) functionalization, and without need for longer C(n)F(2n+1) (n>1) perfluorinated chains. The short intermolecular distance between outer C==C double bonds observed in the layered structure of (E)-1 allows a solid-state [2+2] photocyclization with formation of chiral dyads incorporating the characteristic cyclobutane ring. These dyads containing two dihydrotetrathiafulvalene moieties facing each other exhibit reversible oxidation to the mixed-valence radical cation state and organize in the solid-state into the same layered structures with fluorous bilayers.

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Section: Resultsmentioning

confidence: 99%

Fluorine Segregation in Crystalline Materials: Structural Control and Solid‐State [2+2] Cycloaddition in CF₃‐Substituted Tetrathiafulvalene Derivatives

Jeannin

Fourmigué

2006

Chemistry A European J

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“…Air and/or water-sensitive reactions were conducted under nitrogen using dry, freshly distilled solvents. The synthesis of 5,6-diamino-2-[4,5-bis(alkylthio)-1,3-dithiole-2-ylidene]benzo[d]-1, 3-dithioles (3 a,b ), 2,7-diiodophenanthrene-9,10-dione (4), 1,4-diethynylbezene (6), 1,4-bis[dodecyloxyl)-2,5-diethynylbezene (7) and Fe(bpy) 3 (PF 6 ) 3 (bpy ¼ 2,2 0 -bipyridine)] were prepared according to the literature procedures. [16][17][18][19][20][21] Monomer Synthesis …”

Section: Methodsmentioning

confidence: 99%

“…[6][7][8] So the concept of combining TTF with linear p-conjugated polymers offers exciting potentialities to develop original organic conducting materials. [9] From the viewpoint of polymer physical properties, polymers are well known for their good film-forming property.…”

Section: Introductionmentioning

confidence: 99%

Semiconducting Oligo‐(Aryleneethynylene)s with Coplanarity of Main Chain and Tetrathiafulvalene (TTF) Side Chains: Synthesis, Self‐Assembly, and Conductive Properties

Hou

Yang

Wan

et al. 2009

Macro Chemistry & Physics

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Two oligo‐(aryleneethynylene)s, with coplanarity of main chain and tetrathiafulvalene (TTF) side chains, have been prepared and characterized. The X‐ray diffractions (XRDs) show that their π‐extended coplanar backbones can form continuous π‐stacking. For the two oligomers, one stacks in the inter‐digitation packing mode; another stacks in the end‐to‐end packing mode. Cyclic voltammetries reveal that the two oligomers have almost the same reversible electroactive properties. The TTF units of the two oligomers can be oxidized to TTF.1+ by Fe(bpy)3(PF6)3 (bpy = 2,2′‐bipyridine). The band gaps, deduced from UV‐Vis absorption spectra, are 1.92 and 2.03 eV, respectively. The conductivities of the two oligomers are 1 × 10−5 and 6 × 10−8 S · cm−1 at room temperature. The charge transfer (CT) complexes of the oligomers and tetracyanoquinodimethane (TCNQ) exhibit higher conductivity up to 0.2 S · cm−1.magnified image

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“…Tetrathiafulvalene (TTF) is a unique molecule of paramount importance [13] in materials science due to its π-electron-donating and redox properties, and its conjugates and derivatives find numerous applications, for example, in supramolecular chemistry, [14] molecular electronics [15] and organogels. [16] The conjugates of nucleobases [17] with TTF have been prepared and used for self-assembly in crystals.…”

Section: Introductionmentioning

confidence: 99%

Tetrathiafulvalene‐Labelled Nucleosides and Nucleoside Triphosphates: Synthesis, Electrochemistry and the Scope of Their Polymerase Incorporation into DNA

et al. 2009

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The title 5-substituted pyrimidines (U and C) and 7-substituted 7-deazapurines (7-deazaA and 7-deazaG) bearing tetrathiafulvelene (TTF) attached through an acetylene linker have been prepared by Sonogashira cross-coupling of the corresponding 5-or 7-iodo derivatives of nucleosides with 2-ethynyltetrathiafulvalene. Their subsequent triphosphorylation gave the corresponding nucleoside triphosphates (dNTPs). Square-wave voltammetry of the TTF-labelled nucleosides and nucleotides showed two peaks, one at 0.2-0.3 V and the other at around 0.65 V (vs. Ag|AgCl|3 M KCl), which correspond to two reversible one-electron redox pro-

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Highly Functionalized Tetrathiafulvalenes: Riding along the Synthetic Trail from Electrophilic Alkynes

Cited by 164 publications

References 336 publications

Fluorine Segregation in Crystalline Materials: Structural Control and Solid‐State [2+2] Cycloaddition in CF₃‐Substituted Tetrathiafulvalene Derivatives

Fluorine Segregation in Crystalline Materials: Structural Control and Solid‐State [2+2] Cycloaddition in CF₃‐Substituted Tetrathiafulvalene Derivatives

Semiconducting Oligo‐(Aryleneethynylene)s with Coplanarity of Main Chain and Tetrathiafulvalene (TTF) Side Chains: Synthesis, Self‐Assembly, and Conductive Properties

Tetrathiafulvalene‐Labelled Nucleosides and Nucleoside Triphosphates: Synthesis, Electrochemistry and the Scope of Their Polymerase Incorporation into DNA

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Highly Functionalized Tetrathiafulvalenes: Riding along the Synthetic Trail from Electrophilic Alkynes

Cited by 164 publications

References 336 publications

Fluorine Segregation in Crystalline Materials: Structural Control and Solid‐State [2+2] Cycloaddition in CF3‐Substituted Tetrathiafulvalene Derivatives

Fluorine Segregation in Crystalline Materials: Structural Control and Solid‐State [2+2] Cycloaddition in CF3‐Substituted Tetrathiafulvalene Derivatives

Semiconducting Oligo‐(Aryleneethynylene)s with Coplanarity of Main Chain and Tetrathiafulvalene (TTF) Side Chains: Synthesis, Self‐Assembly, and Conductive Properties

Tetrathiafulvalene‐Labelled Nucleosides and Nucleoside Triphosphates: Synthesis, Electrochemistry and the Scope of Their Polymerase Incorporation into DNA

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Fluorine Segregation in Crystalline Materials: Structural Control and Solid‐State [2+2] Cycloaddition in CF₃‐Substituted Tetrathiafulvalene Derivatives

Fluorine Segregation in Crystalline Materials: Structural Control and Solid‐State [2+2] Cycloaddition in CF₃‐Substituted Tetrathiafulvalene Derivatives