Oxidation of phosphines containing two or three tetrathiafulvalene (TTF) or o-dimethyl-TTF moieties. Evidence for formation of radical polycations

Gerson, Fabian; Lamprecht, Axel; Fourmigué, Marc

doi:10.1039/p29960001409

Cited by 40 publications

(28 citation statements)

References 30 publications

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“…Following this first report, a series of TTFs containing aryl-and alkylphosphines were prepared according to this chemical pathway, by varying the nature of the phosphorus halide, PPh 2 Cl [83], PEt 2 Cl [84], PPhCl 2 [85,86], PEtCl 2 [84] or PBr 3 [86] (Scheme 32), affording a variety of TTF-phosphines, bis(TTF)phosphines and tris(TTF)phosphines. Depending on the amount of base used in the lithiation step, it is possible to form the mono, the bis-(4,4 ) and the tetrakis lithiated species [87].…”

Section: Phosphine Directly Linked To the Donor Corementioning

confidence: 99%

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

Lorcy

Bellec

Fourmigué

et al. 2009

Coordination Chemistry Reviews

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142

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Section: Phosphine Directly Linked To the Donor Corementioning

confidence: 99%

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

Lorcy

Bellec

Fourmigué

et al. 2009

Coordination Chemistry Reviews

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255

142

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“…o-Me 2 TTF was prepared according to a literature method. [21] NMR spectra were recorded on a Bruker Avance DRX 500 spectrometer operating at 500.04 MHz for 1 H and 125.75 MHz for 13 C. Chemical shifts are expressed in parts per million (ppm) downfield from external TMS. The following abbreviations are used: s, singlet.…”

Section: Methodsmentioning

confidence: 99%

Intramolecular Mixed‐Valence State Through Silicon or Germanium Double Bridges in Rigid Bis(Tetrathiafulvalenes)

Biaso

Geoffroy

Canadell

et al. 2007

Chemistry A European J

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The synthesis and characterization of two ortho‐dimethyltetrathiafulvalene (o‐DMTTF)‐based rigid dimers containing dimethylsilicon (Me2Si) or dimethylgermanium (Me2Ge) linkers are described. Single‐crystal X‐ray analysis reveals planar geometry for the central 1,4‐disilicon or 1,4‐digermanium six‐membered rings. DFT calculations provide optimized conformations in agreement with the experimental ones, and also emphasize the role of the heteroatomic linkers in the conjugation between the two redox active units. Cyclic voltammetry measurements show sequential oxidation into radical cation, and then dication species. Solution EPR measurements on the radical‐cation species indicate full delocalization of the unpaired electron over both electroactive TTF units, with an associated coupling of 0.42 G with twelve equivalent protons. DFT calculations afford fully planar geometry for the radical‐cation species and confirm the experimental isotropic coupling constant. Single‐crystal X‐ray analyses of two charge‐transfer compounds obtained upon chemical oxidation, formulated as [(Me2Si)2(o‐DMTTF)2]⋅1/2[TCNQ]⋅1/2[TCNQF4] and [(Me2Ge)2(o‐DMTTF)2]⋅[TCNQ], demonstrate the occurrence of genuine mixed‐valence radical‐cation species, as well as a three‐dimensional network of short S⋅⋅⋅S intermolecular contacts. Temperature‐dependent conductivity measurements demonstrate semiconducting behavior for both charge‐transfer compounds, with an increase of the absolute value of the conductivity upon applying external pressure. Band structure calculations reveal peculiar pseudo‐two‐dimensional electronic structures, also confirming electronic interactions through SiMe2 and GeMe2 bridges.

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“…2 Experimental o-DMTTF was prepared as previously described [15]. Electrocrystallization experiments were performed in CH 3 CN at 1 mA with variable quantities of (i) nBu 4 Br and nBu 4 NI for the (o-DMTTF) 2 (Br) x (I) 1Àx series, and of (ii) nBu 4 Br and Ph 4 PCl for the (o-DMTTF) 2 (Br) x (Cl) 1Àx series.…”

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confidence: 99%

Structural properties of solid solutions of the non‐dimerized, 3/4‐filled conductors (o‐DMTTF)₂X (X = Cl, Br, I)

Reinheimer¹,

Assaf²,

Jeannin³

et al. 2012

Physica Status Solidi (b)

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, Phone/Fax: þ33 223235343Halide salts of the unsymmetrically substituted o-DMTTF, formulated as (o-DMTTF) 2 X, X ¼ Cl, Br, I, are organized into uniform chains in a tetragonal structure with space group I-42d, providing a rare example of non-dimerized 3/4 filled system. Solid solutions formulated as (o-DMTTF)(Br) x (Cl) 1Àx and (o-DMTTF) 2 (Br) x (I) 1Àx have been prepared and structurally characterized. A systematic preferential bromide insertion is observed together with a lateral expansion of the structure with increasing anion size.Tetragonal (space group I-42d) structure of the halide salts of o-DMTTF, in solid solutions (o-DMTTF) 2 (X) x (Y) 1Àx .

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Oxidation of phosphines containing two or three tetrathiafulvalene (TTF) or o-dimethyl-TTF moieties. Evidence for formation of radical polycations

Cited by 40 publications

References 30 publications

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

Intramolecular Mixed‐Valence State Through Silicon or Germanium Double Bridges in Rigid Bis(Tetrathiafulvalenes)

Structural properties of solid solutions of the non‐dimerized, 3/4‐filled conductors (o‐DMTTF)₂X (X = Cl, Br, I)

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Oxidation of phosphines containing two or three tetrathiafulvalene (TTF) or o-dimethyl-TTF moieties. Evidence for formation of radical polycations

Cited by 40 publications

References 30 publications

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

Intramolecular Mixed‐Valence State Through Silicon or Germanium Double Bridges in Rigid Bis(Tetrathiafulvalenes)

Structural properties of solid solutions of the non‐dimerized, 3/4‐filled conductors (o‐DMTTF)2X (X = Cl, Br, I)

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Structural properties of solid solutions of the non‐dimerized, 3/4‐filled conductors (o‐DMTTF)₂X (X = Cl, Br, I)