Electrochemical Synthesis of Extended TTF

Lorcy, Dominique; Carlier, R.; Robert, A.; Tallec, A.; Maguères, Pierre Le; Ouahab, L.

doi:10.1021/jo00113a026

Cited by 96 publications

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“…(Decoalescence was observed for para-substituted phenyls with strong electron-donating groups like Me 2 N-or MeO-. [5,10,11] ) It should be noted that unsymmetrically substituted dendralene-type TTF vinylogs also showed two single-electron oxidation waves. [16,17] On increasing the potential to~1.3 V (vs. Ag/Ag + reference electrode), a third, partly reversible two-electron oxidation wave was observed to form the tetracation 10 4 + (Figure 2a).…”

Section: Resultsmentioning

confidence: 99%

“…[10][11][12] This last set of systems provide very interesting examples of "inverted potentials", [13] whereas the less distorted structure 2 k (R = CN) undergoes two one-electron oxidation processes. [12] Another structural modification to the vinylogous scaffold, which leads to intriguing and more complex multielectron oxidation processes, involves the attachment of one or two redox-active pendant group(s).…”

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“…Although TTF vinylogs that are unsubstituted or symmetrically disubstituted (at the central =C(R) À C(R)= fragment) generally exist with trans arrangements of the dithiole moieties, [10,11] the geometry of the unsymmetrical structure 10 can be substantially dictated by the bulky thioxanthene moiety. For example, TTF vinylogs of type 2, in which two dithiole rings are linked through the aliphatic bridge [2, R= Ph or substituted phenyls; R 1 = Me; (…”

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Remarkable Interplay of Redox States and Conformational Changes in a Sterically Crowded, Cross‐Conjugated Tetrathiafulvalene Vinylog

Amriou¹,

Perepichka²,

Batsanov³

et al. 2006

Chemistry A European J

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Derivatives of 9-[2-(1,3-dithiol-2-ylidene)ethylidene]thioxanthene have been synthesized using Horner-Wadsworth-Emmons reactions of (1,3-dithiol-2-yl)phosphonate reagents with thioxanthen-9-ylidene-acetaldehyde (5). Further reactions lead to the sterically crowded cross-conjugated "vinylogous tetrathiafulvalene" derivative 9-[2,3-bis-(4,5-dimethyl-1,3-dithiol-2-ylidene)-propylidene]thioxanthene (10). X-ray crystallography, solution electrochemistry, optical spectroscopy, spectroelectrochemistry, and simultaneous electrochemistry and electron paramagnetic resonance spectroscopy, combined with theoretical calculations performed at the B3LYP/6-31G(d) level, elucidate the interplay of the electronic and structural properties in these molecules. For compound 10, multistage redox behavior is observed: the overall electrochemical process can be represented by 10-->10(.+)-->10(2+)-->10(4+) with good reversibility for the 10-->10(.+)-->10(2+) transformations. At the tetracation stage there is the maximum gain in aromaticity at the dithiolium and thioxanthenium rings. Theory predicts that for 10, 10(.+), and 10(2+) the trans isomers are more stable than the cis isomers (by ca. 2-18 kJ mol(-1)), whereas for 10(4+) the cis isomer becomes more stable than the trans isomer (by ca. 25 kJ mol(-1)) [trans and cis refer to the arrangement of the two dithiole moieties with respect to the central ==C(R)--C(H)== fragment]. These data explain the detection in cyclic voltammograms of both trans and cis isomers of 10 and 10(.+) during the reduction of 10(4+) at fast scan rates (>100 mV s(-1)) when the cis-trans isomerization is not completed within the timescale of the experiment. The X-ray structure of the charge-transfer complex (CTC) of 10 with 2,4,5,7-tetranitrofluorene-9-dicyanomethylenefluorene (DTeF) [stoichiometry: 10(.+)(DTeF)(2) (.-)2 PhCl] reveals a twisted conformation of 10(.+) (driven by the bulky thioxanthene moiety) and provides a very rare example of segregated stacking of a fluorene acceptor in a CTC.

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Section: Resultsmentioning

confidence: 99%

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Remarkable Interplay of Redox States and Conformational Changes in a Sterically Crowded, Cross‐Conjugated Tetrathiafulvalene Vinylog

Amriou¹,

Perepichka²,

Batsanov³

et al. 2006

Chemistry A European J

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“…The oxidation of the derivatives of 6-(2-thienyl)-1,4-dithiafulvene 4A4C by (p-BrC 6 H 4 ) 3 N¢SbCl 6 in dichloromethane, followed by the reduction with Zn powder in acetonitrile gave the corresponding oxidative coupling products 5A5C in 80 87% yields. 7 However, the similar reaction of 4D did not proceed, which could be due to the presence of electronwithdrawing methoxycarbonyl groups. The VilsmeierHaack formylation of 5A5C was carried out by treatment with POCl 3 in DMF at room temperature, and the bis(formyl) derivatives 6A6C were obtained in 8593% yields.…”

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confidence: 97%

Synthesis and Properties of 1,3-Dithiole[4]dendralenes, in Which Two Thiophene Rings Are Inserted

Nishiwaki¹,

Tezuka²,

Shirahata³

et al. 2011

Chemistry Letters

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Novel 1,3-dithiole[4]dendralene derivatives 3 with two thiophene spacers were synthesized. Cyclic voltammetry and spectroelectrochemistry suggested the dications of most derivatives of 3 have dimeric thiophenequinoid radical cation structures, while tetramethyltetrakis(methoxycarbonyl) derivative 3Bd adopts a vinylogous TTF dication structure.Tetrathiafulvalene (TTF) and its derivatives have attracted much attention as conductive components of molecular conductors, because they have strong electron-donating properties attributed to formation of stable aromatic 1,3-dithiole rings by one-and two-electron oxidation. In the past three decades, various ³-extended TTF systems have been synthesized toward realization of metallic conductivity by reducing on-site Coulomb repulsion in the dicationic state. 1 [n]Dendralenes with multiple 1,3-dithiole rings are expected to adopt novel molecular arrangement as well as unique multistage redox behavior, because they have several conjugated units that are not conjugated with each other due to their nonplanar structure. 24 We have recently reported the synthesis of [3]-and [5]dendralenes 1 and 2 in which one or two thiophene rings were inserted (Chart 1). 5,6 Spectroelectrochemical experiments revealed that two positive charges distribute mainly on the outer extended TTF moieties in 2 2+ and the molecule might not take a thiophenequinoid structure. 6 However, 1 2+ might take a thiophenequinoid structure with high probability.5 In this connection, 1,3-dithiole[4]dendralene 3 with inserted thiophene is of interest as a multistage redox system. For example, the dication of 3 can adopt two plausible structures, namely dimeric thiophenequinoid radical cation (Type I) and vinylogous TTF dication (Type II) as shown in Figure 1. In this letter, we report the synthesis and electrochemical properties of derivatives of 3.The synthesis of 3 was carried out according to Scheme 1. The oxidation of the derivatives of 6-(2-thienyl)-1,4-dithiafulvene 4A4C by (p-BrC 6 H 4 ) 3 N¢SbCl 6 in dichloromethane, followed by the reduction with Zn powder in acetonitrile gave the corresponding oxidative coupling products 5A5C in 80 87% yields.7 However, the similar reaction of 4D did not proceed, which could be due to the presence of electronwithdrawing methoxycarbonyl groups. The VilsmeierHaack formylation of 5A5C was carried out by treatment with POCl 3 in DMF at room temperature, and the bis(formyl) derivatives 6A6C were obtained in 8593% yields. The Wittig or Horner WadsworthEmmons reaction of 6A6C with the corresponding organophosphorus reagent 7 or 8 in the presence of LDA gave the target [4]dendralenes 3 in 2284% yields. 8 Molecular orbital calculations for 3Aa were carried out by density functional theory (DFT) using B3LYP/6-31G(d).9 Its optimized structure is shown in Figure 2. Each thiopheneextended TTF moiety is almost planar, which indicates that two 1,3-dithiole rings in this unit conjugate effectively with each

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“…For example, vinylogous TTF shows lower oxidation potentials and decreasing the difference between the two oxidation potentials compared to TTF due to the reduced coulombic repulsion in the dication species. 30,31 Herein we investigated to produce novel polymers having vinylogous TTF in the main chain by oxidative polymerization. To our knowledge, there is no example of vinylogous TTF containing polymers in the main chain up to date except for insoluble product made by oxidative polymerization of tetrathiapentalene.…”

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Synthesis of Electron-Donating Polymer Having Vinylogous TTF in the Main Chain

Inagi

Naka

Iida

et al. 2006

Polym J

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ABSTRACT:The electron-donating polymer containing vinylogous TTF unit in the main chain was successfully obtained by oxidative polymerization of bisdithiafulvene (bisDTF) (1). The polymer was soluble in common organic solvents such as chloroform and toluene. Structural characterization of the polymer was provided by 1 H and 13 C NMR spectroscopies. The number-average molecular weight of the polymer was estimated as 5,400 by gel permeation chromatographic analysis (chloroform, polystyrene standards). Optical and electrochemical properties of the polymer were studied by UV-vis analysis and cyclic voltammetry. Charge transfer complex of the polymer with tetracyanoquinodimethane (TCNQ) was obtained in a DMSO solution.

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Electrochemical Synthesis of Extended TTF

Cited by 96 publications

References 1 publication

Remarkable Interplay of Redox States and Conformational Changes in a Sterically Crowded, Cross‐Conjugated Tetrathiafulvalene Vinylog

Remarkable Interplay of Redox States and Conformational Changes in a Sterically Crowded, Cross‐Conjugated Tetrathiafulvalene Vinylog

Synthesis and Properties of 1,3-Dithiole[4]dendralenes, in Which Two Thiophene Rings Are Inserted

Synthesis of Electron-Donating Polymer Having Vinylogous TTF in the Main Chain

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