Synthesis and Characterisation of Macrobicyclic Tetrathiafulvalene-Bridged Cage Molecules

Abstract

A series of new macrobicyclic tetrathiafulvalenophanes of type 1 and 2 with three tetrathiafulvalene bridges has been prepared under high‐dilution conditions using a stepwise selective protection‐deprotection of tetrathiafulvalenethiolates. All the macrobicyclic tetrathiafulvalenes, along with the intermediate compounds 5 and 6 and the unexpected tetrathiafulvalene pentamers 17, were studied by cyclic voltammetry. An electrochemical investigation using the Bard‐Anson equation and thin‐layer cyclic voltammetry has been carried out, allowing an estimate of the number of electrons involved in each redox process of these multi‐redox compounds. The X‐ray crystal structure showing the unusual crystal packing of 2a is also presented.

A novel hexakis(tetrathiafulvalene) derivative: synthesis, structure and electrochemical properties

“…As far as we are aware, no compound containing more than three TTF moieties has been structurally studied previously, and the structures of very few tris(TTF) compounds have been reported. [8][9][10][11] Molecule 3 has crystallographic C i symmetry. The central benzene ring is planar, with CH 2 -S bonds directed alternately above and below its plane.…”

Molecular Electrochemistry of Cyclophanes

“…Even more complex molecules, like cage-type TTF-trimers [54], bis(tetrathiafulvalene) cuppedophanes [55] and to a lesser degree a pyrrolo-tetrathiafulvalene cage [56], fit into the same picture. Finally, more recently, "extended" tetrathiafulvalenes were incorporated into cyclophanes, and electrochemically oxidized [57,58].…”

Synthesis Strategies and Chemistry of Nonsymmetrically Substituted Tetrachalcogenafulvalenes

“…Since then, the progress made in the synthesis of such molecules − has been closely related to the discovery of new materials exhibiting conducting, − superconducting, , magnetic, − and optical properties. − More recently the increasing search for solids displaying combined physical properties − and in the construction of supramolecular architectures − such as oligomers, − dendrimers, ,− macrocycles, − and cyclophanes − derived from TTF is largely responsible for the developments underway today in the chemistry of these tetrachalcogenated compounds and, more particularly, of their nonsymmetrical derivatives that are the most frequently involved in the numerous investigations mentioned above. The preparation of these dissymmetric derivatives is primarily carried out using three strategies, as mentioned by Krief 16 (Scheme ): strategy I, based on the double condensation of dichalcogenolate entities with tetrachloroethylene; strategy II, which corresponds to the monocondensation of two 1,3-dichalcogenole rings; and strategy III, which consists of the replacement of one (or several) hydrogen atom(s) in TTF or TSF (tetr...…”