Novel enantiopure bis(pyrrolo)tetrathiafulvalene donors exhibiting chiral crystal packing arrangements

Abstract

Two novel enantiopure bis(pyrrolo|3,4-d|)tetrathiafulvalene i « derivatives, substrates for preparing chirol conducting materials, show chiral crystal packing arrangements in which successive layers are rotated in accordance with an exact or approximate 4 S axis. The corresponding donors containing fused di hydro pyrrole groups, and thus four more hydrogen i5 atoms, form stacks along a crystal axis.bisfpyrrolo [3,4-d]tetrathiafulvalene system and the helical-type 45 chiral packing arrangements of donors 8 and 10, an important stepping stone to the production of electroactive materials with chiral packing arrangements. The preparative route (Scheme) builds on Becher's approach to bisjpyrroloJTTF.

Enantiopure Conducting Salts of Dimethylbis(ethylenedithio)tetrathiafulvalene (DM‐BEDT‐TTF) with the Hexachlororhenate(IV) Anion

“…Moreover, redox modulation of the chiroptical properties of chiral TTFs can be achieved, as in the recently described TTF‐helicenes15 or TTF‐allenes 16. Although, besides the examples already mentioned, several other families of chiral precursors such as hydroxylated BEDT‐TTFs,17 bis(pyrrolo)‐TTFs,18 TTF‐bis(oxazolines),19 TTF‐binaphthyls with axial chirality,20 TTF‐sulfoxides with stereogenic sulfur atoms21 or C 3 ‐symmetric tris(TTFs) that show supramolecular chirality22 have been reported, chiral conducting salts derived therefrom are comparatively less developed, in particular those that contain magnetic ions 5. The combination of conductivity and magnetism has allowed the preparation of molecular magnetic conductors in which the two physical properties can coexist or interplay 23.…”

Order Versus Disorder in Chiral Tetrathiafulvalene‐Oxazoline Radical‐Cation Salts: Structural and Theoretical Investigations and Physical Properties

“…Because the large majority of molecular conductors and superconductors are based on tetrathiafulvalene (TTF) derivatives, [8] a most useful family of organic redox-active molecules, [9] much effort is currently being directed towards the synthesis of enantiopure TTFs [2] with the ultimate goal to produce chiral-conducting materials. Accordingly, several families of chiral TTFs, for example, bis(ethA C H T U N G T R E N N U N G ylA C H T U N G T R E N N U N G enedithio)-tetrathiafulvalene (BEDT-TTF) derivatives, [10] EDT-TTF-oxazolines (EDT = ethylenedithio), [11] EDT-TTF-bis(oxazolines), [12] TTFs with chiral side chains, [13] bisA C H T U N G T R E N N U N G (pyrrolo)-TTFs, [14] and TTF-sulfoxides, [15] have been described (Figure 1). …”

Tetrathiafulvalene‐[2.2]paracyclophanes: Synthesis, crystal structures, and chiroptical properties

“…A particularly useful electroactive unit to be introduced into chiral systems is tetrathiafulvalene (TTF), 14 as it has previously provided chiral conductors in which differences of conductivity have been observed between the enantiopure and racemic forms due either to structural disorder [15][16][17] or different packings. 20 While strategies based on stereogenic centers, [21][22][23][24][25][26] axial chirality, [27][28][29][30] helical [This article is part of the Special Issue: Proceedings 16th International Conference on Chiroptical Spectroscopy, Rennes France 2017. 20 While strategies based on stereogenic centers, [21][22][23][24][25][26] axial chirality, [27][28][29][30] helical [This article is part of the Special Issue: Proceedings 16th International Conference on Chiroptical Spectroscopy, Rennes France 2017.…”