Tetrathiafulvalene synthesis

Moore, A. J., Goldenberg, L. M., Bryce, M. R., etal, New crown annelated tetrathiafulvalenes Synthesis, electrochemistry, self-assembly of thiol derivatives, and metal cation recognition. J. Org. Chem. 2000, 65, 8269-8276. 

Tetrathiafulvalenes, synthesis, chemical and physical properties of 87MI61. 

Tetrathiafulvalenes, synthesis, properties of 87MI61. Tetrachalcogenofulvalenes and their charge-transfer complexes, conducting properties and nature of heteroatoms 87YGK502. 

Whereas the fulvalenes 1-6 are relatively unstable hydrocarbons and therefore largely of theoretical interest, their heteroatom analogs demand considerable attention in synthetic chemistry and material sciences. Tlie general principle of heterocyclic chemistry to relate heterocyclic compounds to carbocyclic ones was the driving force for the synthesis and their application to heteroful-valenes. Numerous heterocyclic derivatives iso-rr-electronic with, for example, heptafulvalene 3 were accessible in which pairs of carbon atoms linked by double bonds were replaced by heteroatoms capable of contributing two tt-electrons. By this principle, the well-known tetrathiafulvalene and its derivatives have been synthesized successfully (Scheme 2). 

Advances in synthesis and research of oligomeric tetrathiafulvalenes 97MI9. Enantioselective oxidation of 1,3-dithiolanes to corresponding S-oxides and S,S-dioxides by designer yeast 99JHC1533. 

Synthesis of tetrathiafulvalene derivatives for the creation of new organic functional materials 98YGK755. 

The high level of activity in the synthesis of tetrathiafulvalenes (TTFs) and related systems has continued and several major reviews of the area have appeared <95AHC(62)249, 95MI1481,96SR(18)1>. A mechanistic study on the P(III) mediated coupling of 1,3-dithiole-... 

Jorgenson et al. reported [125] the synthesis of bolaamphiphile 46 in which a tetrathiafulvalene (TTF), a substrate currently of importance in fields such as organomagnetism and molecular electronics, was incorporated within the central lipophilic region. Gel formation of 46 (Fig. 20) in either DMF-water or ethanol-water solution was noted which bear similarities with the above findings of Newkome and coworkers. 

In recent years, the amount of research time devoted to materials chemistry has risen almost exponentially and sulfur-based radicals, such as the charge-transfer salts based upon TTF (tetrathiafulvalene), have played an important role in these developments. These TTF derivatives will not be discussed here but are dealt with elsewhere in this book. Instead we focus on recent developments in the area of group 15/16 free radicals. Up until the latter end of the last century, these radicals posed fundamental questions regarding the structure and bonding in main group chemistry. Now, in many cases, their thermodynamic and kinetic stability allows them to be used in the construction of molecular magnets and conductors. In this overview we will focus on the synthesis and characterisation of these radicals with a particular emphasis on their physical properties. 

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. 

The convergent synthesis of a range of aryl ester dendrimers with peripheral tetrathiafulvalene units was also reported (Devonport et al. 1998). The dendrimers acquire some amount of the cation-radical tetrathiafulvalene tips on reacting with iodine in solutions. Another promising material is polyphenylene dendrimers functionalized with benzophenone units. On being transformed into the potassium ketyl derivatives, the dendrimers bring forth intermolecular biradicals. These technically attractive species contain four-membered cycles that coordinatively combine two potassium cations... 

The synthesis of the triazolino[4, 5 l,2][60]fullerene 204, a novel donor-acceptor dyad exhibiting efficient electron-transfer dynamics, was reported by Guldi et al. (44) (Scheme 9.44). The azido tetrathiafulvalene 203, on heating with [60]fullerene in o-dichlorobenzene at 60 °C, gave the triazoline 204 in 24%... 

Muller and co-workers have prepared the first reported tetrathiafulvalene (TTF) main chain polymer which they suggest may improve metallic and redox properties of the material due to improved through-bond and through-space interactions in the solid state <1999CC1407>. They also report a simple synthesis of the polymeric material via a novel oxidative polymerisation sequence as outlined in Scheme 18. 

Macrocyclic tetrathiafulvalenophanes have recently been prepared (80AG(E)66, 67) by a variation of the synthesis of tetrathiafulvalene (74JOC3608) via a high dilution intramolecular cyclization. 

Apart from thiolate ligands, S, Se or -containing fulvalene derivatives have been employed as electron donors in the synthesis of gold complexes. The combination of tetrathiafulvalene, TTF, with the gold complex bis(pyrazine-2,3-diselenolate)aurate... 

The synthesis of organic metals containing either a tetrathiafulvalene (TTF) system255 or a trimethylenemethane (TMM) system256 (equation 26) has been accomplished by thionation with P4S10. 

The convergent synthesis of a range of aryl ester dendrimers with peripheral tetrathi-afulvalene units was also reported (Devonport et al. 1998). The dendrimers acquire some amount of the cation radical tetrathiafulvalene tips upon reaction with iodine in solutions. 

The group of Professor Nazario Martin developed the synthesis of several donor-acceptor arrays containing -conjugated oPPEs of different length linking -extended tetrathiafulvalene (exTTF) as electron donor and C o as electron acceptor. Thereby, they systematically increased the length of the molecular wire from the monomer to the trimer. A detailed description of the corresponding synthesis is described elsewhere [8]. 

Jprgensen et al. 141 utilized this molecular organization process (dumbbell-like stacking) to incorporate tetrathiafulvalene (TTF a substrate currently of interest in such areas as molecular electronics and organomagnetism) within the central lypophilic region (Scheme 4.33) of the self-assembled, supramolecular structures. A multistage synthesis... 

Dithiolo-l,2-dithioles, thermolysis and photolysis of 91PS(58)179. Structure of trithispentalenes and related compounds 91PS(58)17. Synthesis and properties of new functionalized tetrathiafulvalene jr-... 

Another example results from the synthesis of compound (53) which contains the structural elements of a tetrathiafulvalene and of a quinodimethane. Thus treatment of the bis Grignard reagent of (50) with the 1,3-benzodithiolylium perchlorate (51) leads to (52) which is converted into (53) by subsequent treatment with trityl fluoroborate and triethyl-amine <80AG(E)204>. 

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