Activation of C−H⋅⋅⋅Halogen (Cl, Br, and I) Hydrogen Bonds at the Organic/Inorganic Interface in Fluorinated Tetrathiafulvalenes Salts

Dautel, Olivier; Fourmigué, Marc; Canadell, Enric

doi:10.1002/1521-3765(20010618)7:12<2635::aid-chem26350>3.0.co;2-7

Cited by 38 publications

(25 citation statements)

References 31 publications

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“…Single-crystal X-ray diffraction measurements revealed the recurrent formation of layered structures with a strong segregation of the fluorinated moieties and formation of fluorine bilayers [32–33], attributed to the amphiphilic character of those TTF derivatives upon CF 3 -functionalization. A strong anodic shift of the first oxidation potential was also noted for 1c and 2cc , when compared with the unsubstituted EDT-TTF molecule.…”

Section: Introductionmentioning

confidence: 99%

Trifluoromethyl-substituted tetrathiafulvalenes

Jeannin¹,

Barrière²,

Fourmigué³

2015

Beilstein J. Org. Chem.

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SummaryA series of tetrathiafulvalenes functionalized with one or two trifluoromethyl electron-withdrawing groups (EWG) is obtained by phosphite coupling involving CF3-substituted 1,3-dithiole-2-one derivatives. The relative effects of the EWG such as CF3, CO2Me and CN on the TTF core were investigated from a combination of structural, electrochemical, spectrochemical and theoretical investigations. Electrochemical data confirm the good correlations between the first oxidation potential of the TTF derivatives and the σmeta Hammet parameter, thus in the order CO2Me < CF3 < CN, indicating that, in any case, the mesomeric effect of the substituents is limited. Besides, crystal structure determinations show that the deformation of the unsymmetrically substituted dithiole rings, when bearing one, or two different EWG, and attributed to the mesomeric effect of ester or nitrile groups, is not notably modified or counter-balanced by the introduction of a neighboring trifluoromethyl group. DFT calculations confirm these observations and also show that the low energy HOMO–LUMO absorption band found in nitrile or ester-substituted TTFs is not found in TTF-CF3, where, as in TTF itself, the low energy absorption band is essentially attributable to a HOMO→LUMO + 1 transition. Despite relatively high oxidation potentials, these donor molecules with CF3 EWG can be involved in charge transfer complexes or cation radical salts, as reported here for the CF3-subsituted EDT-TTF donor molecule. A neutral charge transfer complex with TCNQ, (EDT-TTF-CF3)2(TCNQ) was isolated and characterized through alternated stacks of EDT-TTF-CF3 dimers and TCNQ in the solid state. A radical cation salt of EDT-TTF-CF3 is also obtained upon electrocrystallisation in the presence of the FeCl4 − anion. In this salt, formulated as (EDT-TTF-CF3)(FeCl4), the (EDT-TTF-CF3)+• radical cations are associated two-by-two into centrosymmetric dyads with a strong pairing of the radical species in a singlet state.

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Section: Introductionmentioning

confidence: 99%

Trifluoromethyl-substituted tetrathiafulvalenes

Jeannin¹,

Barrière²,

Fourmigué³

2015

Beilstein J. Org. Chem.

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“…6). 89,90 (A similar mode of association has been observed for the IBr 2 -salt of the bis(1,4,6-trithiepinyl)TTF 175. 81,85 ) The adjacent fluorines and the donor's positive charge promote the hydrogen bonding potential of the methylene groups.…”

Section: Et Analogues With Expanded Outer Ringsmentioning

confidence: 99%

“…In the 2:1 salt of 174 with Mo 6 Cl 14 2-two donors act as pincers forming hydrogen bonds to chlorines of the complex anion. 89,90 Fourmigué has also described an interesting 1:2 mixed valence salt of 174 with the isosteric dithiolene anion 176, 91 and a 1:1 charge transfer salt of the difluoro donor 173 with TCNQF 4 has been described in which pairs of donors and pairs of acceptors form a pseudo κ-phase. 92 Donor 177 which has five sulfur atoms in an outer seven membered ring has been reported along with its perchlorate salt.…”

Section: Et Analogues With Expanded Outer Ringsmentioning

confidence: 99%

Substituted BEDT‐TTF Derivatives: Synthesis, Chirality, Properties and Potential Applications

Wallis

Griffiths

2005

ChemInform

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Abstract.The increasing availability of functionalized BEDT-TTF derivatives in both racemic and enantiopure forms opens up great opportunities for preparing multifunctional materials and chiral conducting systems in the form of crystals, thin films and polymers. Functionalities such as amino and carboxyl will allow attachment to other molecular systems, while intermolecular interactions between substituents, e.g. hydrogen bonding and halegon---halegon interactions, provides additional tools for designing solid state radical cation structures. In this review the syntheses of substituted derivatives of BEDT-TTF and closely related donors are surveyed, along with the structures and properties of the radical cation salts so far prepared, as a stimulus for future application of these versatile and attractive molecules. Particular attention is paid to the preparation of single enantiomers, and to the stereochemical consequences of the synthetic procedures. IntroductionOrganosulfur donor molecules have been a major focus for research in the preparation of molecular conducting systems, with tetrathiafulvalene 1 and its derivatives playing a leading role initially.1 However, breakthroughs in the last decade for preparing superconducting and hybrid materials have featured bis(ethylenedithio)tetrathiafulvalene 2, also known as BEDT-TTF or ET.2 This molecule shows two reversible oxidations at 0.50 and 0.91 V relative to the Ag/AgCl electrode, ca. 0.15 V more positive than those for TTF, and has been converted into a very large number of radical cation salts. These have been studied by a wide range of techniques stimulated in part by formation of superconducting radical cation salts with anions Cu(NCS) 2

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“…[144] Planar molecules such as TTF-derivatives are also good candidates, since they can be functionalized and thus control over the p-stacking and the architecture can be achieved. [20,23] Recently, conductance modulation has been demonstrated with FETs based on SAMs, thus evidencing gain for electronic transport perpendicular to a single molecular layer. [145] In fact, electrons with energies above~0.8 eV can be transmitted without alteration through an organic layer with a thickness of about 100 .…”

Section: Doping: Charge Transfer and Charge Injectionmentioning

confidence: 99%

“…[21] In general, the functionalization of TTF and TSF derivatives permits the correlation of the collective electronic properties of their CT salts with defined structural features, in order to ultimately be able to control and manipulate both the structure and the properties of the system. [20,22,23] The same principle should apply to other molecules as it does, for instance, to C 60 and oligothiophenes. [24] A variety of applications are foreseen for MO materials, especially in the form of thin films with effective areas larger than those achieved for the rather small single crystals.…”

Section: Introductionmentioning

confidence: 99%

Perspectives on Thin Molecular Organic Films

Fraxedas¹

2002

Adv. Mater.

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The engineering versatility of molecular organic materials, together with their attractive electronic, magnetic, and optical properties, have triggered their preparation as thin films in the last years. Although the interactions between molecules and inorganic substrates are rather weak (van der Waals, hydrogen bonding, etc.), the crystallographic phase, the type and degree of orientation, and the morphology of the resulting films critically depend on the interface and the kinetics of growth. The control of the structure and morphology of the films is thus essential when envisioning practical applications. The relevance of interfaces in the growth and doping of films is discussed, and the phenomenology of polymorphism is explored. Additional issues such as the mechanical properties are also addressed. The figure, showing a scanning tunneling microscopy image of a monolayer of bis(ethylenedithio)‐tetrathiafulvalene on a Au(111) substrate, illustrates the interface issue.

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Activation of C−H⋅⋅⋅Halogen (Cl, Br, and I) Hydrogen Bonds at the Organic/Inorganic Interface in Fluorinated Tetrathiafulvalenes Salts

Cited by 38 publications

References 31 publications

Trifluoromethyl-substituted tetrathiafulvalenes

Trifluoromethyl-substituted tetrathiafulvalenes

Substituted BEDT‐TTF Derivatives: Synthesis, Chirality, Properties and Potential Applications

Perspectives on Thin Molecular Organic Films

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