Synthesis and Characterization of Novel Tetrathiafulvalene‐Type Electron Donors Bearing Two Pyridine Groups

Abstract

International audienceThe syntheses of seven new tetrathiafulvalene (TTF) derivatives substituted by two pyridine groups and their characterization by the usual methods are described. Cyclic voltammetry of all the compounds showed two one-electron reversible waves with redox potentials comparable to other pyridine-substituted TTF molecules. X-ray crystal structures were solved for five compounds. In all the molecular structures the pyridine groups lie out of the central TTF plane but are located on the same side of that plan

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

“…It is worth noting that according to the second strategy and starting from bis(cyanoethylseleno)TTF derivatives, the corresponding TTFs 57 and 58 bearing two 3-or 4-pyridyl groups linked to the selenium atom have been synthesized [43]. It can be observed that, for all these derivatives, the substitution of the pyridine ring in either the ortho, meta or para position has no effect on the redox potential values (Table 5).…”

“…An extensive series of bis(pyridylmethylthio)-TTF derivatives 51-59 was prepared by two different routes (Scheme 15): (i) unsymmetrical phosphite coupling involving a pyridylfunctionalized 1,3-dithiole-2-one molecule or (ii) alkylation of a TTF dithiolate with the appropriate halomethylpyridine derivative [42][43][44][45][46]. It is worth noting that according to the second strategy and starting from bis(cyanoethylseleno)TTF derivatives, the corresponding TTFs 57 and 58 bearing two 3-or 4-pyridyl groups linked to the selenium atom have been synthesized [43].…”

Coordination assemblies based on a flexible tetrathiafulvalene derivative

“…The synthesis of 1 has been reported by homo-coupling of the corresponding dithiolone with triisopropyl phosphite in 42% yield. [26] We have followed an alternative pathway, as described for mono-or di-functionalized analogues, [31][32][33] consisting in the deprotection under basic conditions of propionitrile-appended TTF 2, prepared as described, [27] followed by reaction with 4-(chloromethyl)pyridine hydrochloride, thus affording 1 in 56% yield after purification (Fig. 2).…”

2,3-Bis(2-cyanoethylsulfanyl)-6,7-tetramethylenetetrathiafulvalene

“…For the synthesis of the title compound, see: Binet et al (1996). Analogous precursors are used to obtain functionalized TTF derivatives (Legros et al, 2000;Benbellat et al, 2006) and oligo-TTF (Carcel et al, 2006).…”