Synthesis Strategies and Chemistry of Nonsymmetrically Substituted Tetrachalcogenafulvalenes

Fabre, Jean‐Marc

doi:10.1021/cr0306440

Cited by 116 publications

(50 citation statements)

References 263 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A common procedure to build the TTF skeleton involves dimerization-desulfurization of 1,3-dithiol-2-thiones in the presence of trialkyl phosphite. [21] In our case, no coupling product was observed on refluxing 6 or 7 with triethyl phosphite. This problem was solved by converting the thioxo reagents to their oxo analogues 8 and 9 with mercuric acetate in chloroform/acetic acid (Scheme 2).…”

Section: Resultsmentioning

confidence: 43%

Bis(calixcrown)tetrathiafulvalene Receptors

Blesa

Zhao

Allain

et al. 2006

Chemistry A European J

View full text Add to dashboard Cite

A new class of electroactive receptors has been synthesized, built by covalent association of five subunits: two calixarene platforms for spatial organization, two polyether 3D cavities for cation binding, and one electroactive TTF unit to probe the complexation event. Sodium complexation induces rigidification of the molecular assembly, as shown by 1H NMR titration and single-crystal X-ray crystallographic studies on free receptor 14 and a corresponding complex with two bound sodium atoms per receptor (15-(NaPF6)2). The calixarene units in these receptors change from a pinched cone conformation in the free ligand to a symmetrical cone in the complex. Cyclovoltammetric studies validated the electrochemical recognition concept of these five-member assemblies.

show abstract

Section: Resultsmentioning

confidence: 43%

Bis(calixcrown)tetrathiafulvalene Receptors

Blesa

Zhao

Allain

et al. 2006

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…The synthesis of CNB-EDT-TTF 3 was obtained under a general route to prepare non-symmetrically substituted TTF derivatives by cross coupling of two different 1,3-dichalcogenole-2-chalconegones [14–15], involving the coupling between 2-thioxobenzo[ d ][1,3]dithiole-5-carbonitrile ( 1 ) [16] and 5,6-dihydro[1,3]dithiolo[4,5- b ][1,4]dithiin-2-one ( 2 ) in 1:1.1 ratio in pure triethyl phosphite during 4 hours at 130 °C leading to the formation of 3 in relatively high yield (63%) (Scheme 1). This coupling reaction also gives rise to smaller amounts of BEDT-TTF (14% yield) and dicyanodibenzene tetrathiafulvalene (dcdb-TTF) [13] as byproducts resulting from homocoupling reactions.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and characterization of the cyanobenzene-ethylenedithio-TTF donor

Oliveira¹,

Belo²,

Santos³

et al. 2015

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

SummaryA dissymmetric TTF-type electron donor, cyanobenzene-ethylenedithio-tetrathiafulvalene (CNB-EDT-TTF), was obtained in high yield, by a cross-coupling reaction with triethyl phosphite between 2-thioxobenzo[d][1,3]dithiole-5-carbonitrile and 5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-one. This new donor was characterized namely by single crystal X-ray diffraction, cyclic voltammetry, NMR, UV-visible and IR spectroscopy.

show abstract

“…[8] Results and Discussion Synthesis: The synthesis of macrocycle 1 d was accomplished by using the route outlined in Scheme 1. After consulting the literature about the preparation of nonsymmetrically substituted TTFs, [11] we decided to prepare the 4,5-diethynyl-A C H T U N G T R E N N U N G ated, 4',5'-dihexyl-substituted 2 d by a Horner-WadsworthEmmons condensation, which avoids formation of unwanted symmetrically substituted TTF.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characteristics of a Nonaggregating Tris(tetrathiafulvaleno)dodecadehydro[18]annulene

Andersson

Kilså

Hassenkam

et al. 2006

Chemistry A European J

View full text Add to dashboard Cite

A new tris(tetrathiafulvaleno)dodecadehydro[18]annulene with six peripheral n-hexyl substituents was prepared by oxidative Glaser-Hay cyclization of a corresponding diethynylated tetrathiafulvalene (TTF) precursor. The electronic properties of the neutral and oxidized species were studied by both UV/Vis absorption spectroscopy and electrochemistry. From these studies, it transpires that the strongly violet-colored macrocycle does not aggregate in solution to any significant degree, which was confirmed by (1)H NMR spectroscopy. This reluctance towards aggregation contrasts that observed for related TTF-annulenes containing other peripheral substitutents. Oxidation of the TTF-annulene occurs in two three-electron steps as inferred from both the peak amplitudes and the spectroelectrochemical study. We find that the tris(TTF)-fused dehydro[18]annulene is more difficult to oxidize (by +0.20 V) than the silyl-protected diethynylated mono-TTF precursor. In contrast, the first vertical ionization energy calculated at the B3 LYP/6-311+G(2d,p) level for the parent tris(TTF)-fused dehydro[18]annulene devoid of peripheral hexyl substituents is in fact lower (by 0.44 eV). Moreover, the surface morphology of 1 d drop-cast on a mica substrate was investigated by atomic force microscopy (AFM). Crystalline domains with slightly different orientations were observed. The thickness of individual layers seen in the crystalline domains and the thickness of a monolayer obtained from a very dilute solution were determined to 1.8-1.9 nm. This thickness corresponds to the diameter of the macrocycle and the layers seen in the film are apparently formed when the molecules stack in the horizontal direction relative to the substrate.

show abstract

Synthesis Strategies and Chemistry of Nonsymmetrically Substituted Tetrachalcogenafulvalenes

Cited by 116 publications

References 263 publications

Bis(calixcrown)tetrathiafulvalene Receptors

Bis(calixcrown)tetrathiafulvalene Receptors

Synthesis and characterization of the cyanobenzene-ethylenedithio-TTF donor

Synthesis and Characteristics of a Nonaggregating Tris(tetrathiafulvaleno)dodecadehydro[18]annulene

Contact Info

Product

Resources

About