Preparation and reactions of bifunctionalized tetrathiafulvalenes

Pittman, Charles U.; Narita, Mao; Liang, Yuan

doi:10.1021/jo00879a013

Cited by 73 publications

(30 citation statements)

References 16 publications

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“…[TBA] 4 TTFTA is synthesized by slightly modifying a previously reported protocol and is shown to be very soluble in common organic solvents such as chloroform and acetonitrile. 22,23 Using cyclic voltammetry, we find two one-electron redox couples, centered about À4.64 and À4.96 eV vs vacuum, respectively, which correspond to the stepwise formation of a radical cation and dication, stabilized by the gain in heteroaromaticity (see Figure 2a). Qin et al have reported redox couples of À4.91 and À5.28 eV vs vacuum for Na 4 TTFTA.…”

Section: Resultsmentioning

confidence: 99%

“…20,21 Particularly suitable as a building block in more complex molecular structures is the tetracarboxylate derivative (TTFTA 4À ) due to its relatively facile synthesis and robustness toward air. 22,23 As such, TTFTA 4À has been applied as a coordinating ligand in metal complexes and 3D-coordination polymers. 24À26 In terms of conjugates of inorganic nanoparticles and derivatives of TTF, we note two studies of TTFÀtetrathiolate crosslinked CdSe and Au nanocrystals.…”

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confidence: 99%

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PbS Nanoparticles Capped with Tetrathiafulvalenetetracarboxylate: Utilizing Energy Level Alignment for Efficient Carrier Transport

et al. 2014

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We fabricate a field-effect transistor by covalently functionalizing PbS nanoparticles with tetrathiafulvalenetetracarboxylate. Following experimental results from cyclic voltammetry and ambient-pressure X-ray photoelectron spectroscopy, we postulate a near-resonant alignment of the PbS 1Sh state and the organic HOMO, which is confirmed by atomistic calculations. Considering the large width of interparticle spacing, we observe an abnormally high field-effect hole mobility, which we attribute to the postulated resonance. In contrast to nanoparticle devices coupled through common short-chained ligands, our system maintains a large degree of macroscopic order as revealed by X-ray scattering. This provides a different approach to the design of hybrid organic-inorganic nanomaterials, circumvents the problem of phase segregation, and holds for versatile ways to design ordered, coupled nanoparticle thin films.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

PbS Nanoparticles Capped with Tetrathiafulvalenetetracarboxylate: Utilizing Energy Level Alignment for Efficient Carrier Transport

et al. 2014

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“…[20] The characterization of the molecular assemblies on surfaces was performed by AFM on a commercial scanning force microscope PiscoSPM from Molecular Imaging operating in air at room temperature. UV/ Vis spectra were recorded using a Varian Cary 05E spectrophotometer.…”

Section: Methodsmentioning

confidence: 99%

Influence of Intermolecular Interactions on the Formation of Tetra(carbomethoxy)‐tetrathiafulvalene Assemblies

et al. 2007

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We study the assemblies that tetra(carbomethoxy)tetrathiafulvalene (TCM-TTF) forms in solution and when deposited on a surface depending on intermolecular interactions and on the interactions with the substrate and the solvent. Its organization on graphite and mica substrates was studied by atomic force microscopy, and different molecular assemblies were observed depending on the prevailing interactions. The promotion of molecule-molecule interactions gave rise to the formation of molecular fibers. The investigation of the influence of the solvent-molecule interactions on TCM-TTF molecular organizations was carried out by UV/Vis spectroscopy, and a new TCM-TTF polymorph was obtained by changing the nature of the solvent. Finally, an explanation for all these phenomena, supported by computational modeling, is put forward.

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“…The pure compound was obtained by filtration of the solution in dichloromethane, followed by evaporation of solvent and preparative chromatography over silica gel. The product was characterized by IR, 1 H NMR, and 13 C NMR spectroscopy.…”

Section: Source Of Materialsmentioning

confidence: 99%

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Crystal structure of 4-methoxycarbonyl-1,3-dithiole-2-thione, C5H4O2S3

Darviche¹,

Asghari²,

Parsapour³

et al. 2007

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialIn the literature 4-methoxycarbonyl-1,3-dithiole-2-thione was obtained in three steps [1]. In the present one-pot synthesis the title compound was obtained under solvent free conditions catalyzed by potassium cyanide in the presence of silica as solid support at 200°C (85 % yield). 0.2 mmol of 4,5-bis(carbonylmethoxy)-1,3-dithiole-2-thione, 0.4 mmol of potassium cyanide and 0.2 g of silica were mixed in a mortar. This powder was heated for 1 h at 200°C. The color of the mixture was turned from yellow to light brown. The pure compound was obtained by filtration of the solution in dichloromethane, followed by evaporation of solvent and preparative chromatography over silica gel. The product was characterized by IR, 1 H NMR, and 13 C NMR spectroscopy. Experimental detailsThe X-ray reflections were rather broad and diffuse, but the data turned out to be useable. All hydrogen atoms were treated using appropriate riding models. The bad quality of the crystals and the dataset were the reasons for the large R values. DiscussionEver since the discovery of the first metallic charge transfer complex composed of TTF (tetrathiafulvalene) and TCNQ (tetracyanoquinodimethane) [2], modifications of the TTF skeleton have received considerable attention from synthetic chemists in exploration of new molecular-based organic metals. Phosphite cross-couplings for the preparation of functionalized TTF derivatives were first investigated because this method is generally simple when yields are good and when products are separable [3][4][5][6]. Thus the interest in the synthesis of various 1,3-dithiole-2-chalcogenone is evident, and promoted us to take up this project. As expected the interatomic distances determined in the 1,3-dithiole-2-thione unit are all similar to analogous values known from the literature. The heterocyclic five-membered dithiolethione ring is planar, and also the carboxyl group stands in the same plane, thus is completely in conjugation. The crystal packing is dominated by very short sulfur···sulfur contacts involving two of the three sulfur atoms and building two-dimensional double layers of molecules. The S1···S1 contacts with 3.51 Å, the S1···S2 contacts with 3.55 Å, and the S2···S2 contacts with 3.42 Å are much shorter than the sum of the van der Waals radii of 3.7 Å [8].

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Preparation and reactions of bifunctionalized tetrathiafulvalenes

Cited by 73 publications

References 16 publications

PbS Nanoparticles Capped with Tetrathiafulvalenetetracarboxylate: Utilizing Energy Level Alignment for Efficient Carrier Transport

PbS Nanoparticles Capped with Tetrathiafulvalenetetracarboxylate: Utilizing Energy Level Alignment for Efficient Carrier Transport

Influence of Intermolecular Interactions on the Formation of Tetra(carbomethoxy)‐tetrathiafulvalene Assemblies

Crystal structure of 4-methoxycarbonyl-1,3-dithiole-2-thione, C5H4O2S3

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