Polymer tetrathiafulvalenes containing

Previous work on the synthesis of TTF (tetrathiafulvalene) containing polymers has been reported by at least seven groups of researchers. Most of this work concerns condensation 6,7,8,9 polymers or polymers made from vinyl substituted TTF molecules . Without exception, the polymers produced by these methods have been largely unacceptable for subsequent physical study because of their brittle,intractable, highly insoluble nature. Only by reaction of a suitably monofunctionalized TTF derivative with the preformed polymer poly(vinylbenzylchloride) has it been found possible — to prepare soluble TTF homopolymers with more manageable physical properties. 

Redox polymer — Redox polymers contain electrostatically and spatially localized redox sites, which can be oxidized or reduced. The redox polymers can be divided into subclasses 1) polymers that contain covalently attached redox sites, either built in the chain or as a pendant group. The redox centers may be organic molecules (e.g., tetrathiafulvalene, tetra-cyanoquinodimethane), organometallic molecules (e.g., - ferrocene), or co or dinative ly attached redox couples (e.g., polymerized metal bipyridine(bpy) complexes) 2) ion-exchange polymeric systems, where the redox-active ions are held by electrostatic binding (e.g., Fe(CN)g- 4- in protonated poly(vinylpiridine) or Ru(bpy)j+/2+ in -> Nafion [i]. 

Despite their inherent electronic advantages, CT complexes and radical cation salts tend to be brittle and unprocessable. This problem might be overcome by the incorporation of oligomeric tetrathiafulvalenes in polymers, whereby the TTFs can be part of a main-chain or side-chain polymer. The key concern thereby is to achieve the suitable packing of the donor moieties, which is, of course, less perfect than in the crystalline state. Remarkably, the rigid-rod poly-TTF 164 could be made recently by a precursor route in which 164 is made by dimethyl disulfide extrusion of the precursor polymer (scheme 39). The electrical conductivity after iodine doping amounts to 0.6 S/cm [221]. Other examples of TTF-containing polymers, either in the backbone [222] or in the side-chain [223], are summarized in chart 25. 

Triethyl phosphite induces intramolecular coupling of two 2-thioxo-3,5-dithiole units to give the tetrathiafulvalene (6) (Scheme 1) <92JCS(Pi)2907>. Treatment of oc,o>-di(episulfides) with Lewis acids, such as SnCl4, yields macrocycle-containing polymers, but with little regiocontrol <84Mi 930-02>. 

EDOT monomers bearing w-iodo-alkyl and w-iodo-polyether side chains (80) have been electro-polymerized into corresponding polymers. These polymers can be rapidly and quantitatively converted into functionalized polymers under mild conditions by postpolymerization reaction with functional blocks bearing a thiolate group, as demonstrated in the case of tetrathiafulvalene (81) [ 151 ]. Application of the same procedure led to a modified electrode containing a tetrathiafulvalene core substituted by two polyether chains (82). It was shown that the binding of Pb by the polymer 82 could be electrochemicaUy driven [185]. 

Tetrathiafulvalene (TTF) is known in supramolecular chemistry for its many charge-transfer complexes [77, 78]. TTF-containing polymers [79] or... 

Hertler WR (1976) Charge-transfer polymers containing 7,7,8,8-tetracyanoquinodimethan and tetrathiafulvalene. J Org Chem 41 1412-1416... 

Yamamoto T, Shimizu T (1997) New it-conjugated polymers containing tetrathiafulvalene as the monomeric unit. J Mater Chem 7 1967-1968... 

Yzambart G, Fabre B, Camerel F, Roisnel T, Lorcy D (2012) Controlled grafting of tetrathiafulvalene (TTF) containing diacetylenic units on hydrogen-terminated silicon surfaces from redox-active TTF monolayer to polymer films. J Phys Chem C 116 12093-12102... 

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