Dithiafulvenes

When treated with sodium disulfide in ethanol, deca-2,4,6,8-tetrayne (53) gives dithiafulvene 54 rather than 1,2-dithiins 55 (67CB107). 

The poly(cyclodiborazane)s containing a dithiafulvene unit in the backbone were also reported (scheme 25).38 This polymer showed an efficient extension of conjugation between the consecutive repeat units due to the strong electron donating property of the dithiafulvene unit. Before doping, this polymer exhibited an electrical... 

Uemura, T., Naka, K. and Chujo, Y. Functional Macromolecules with Electron-Donating Dithiafulvene Unit. Vol. 167, pp. 81-106. 

Keywords Dithiafulvene -Conjugated polymer Dendrimer Polyrotaxane Thioketene dimer... 

Conjugated Dithiafulvenes in Polymer Main-Chain System. 84... 

A dithiafulvene (1) can form a 1,3-dithiolium cation by an easy one-electron oxidation, as a result of its electron-donating property. The 1,3-dithiolium ion is an unsaturated five-membered-ring cation in which each sulfur atom contributes a pair of 3n electrons and, consequently, would be expected to show aromatic stability [1, 2]. The chemistry of the dithiafulvene and its... 

Dithiafulvene derivatives behave as -electron donors and form stable charge-transfer complexes and radical ion salts with a wide variety of organic and inorganic acceptor species. 

Oxidative dimerizations of the dithiafulvenes by both cyclic voltammetry (CV) and chemical method afford dimeric dications (Scheme 1) [6-11]. 

The oxidation potentials can be finely tuned by the attachment of substituents. Delocalized -electron systems of the dithiafulvenes show low oxidation potentials however, non-conjugated dithiafulvenes are typically oxidized at between Fox+0.9 and +1.4 V. Electron-sufficient and deficient substituents on the dithiafulvenes also affect the potentials. 

Dithiafulvenes undergo attack by electrophiles at the exocyclic carbon to give 6-substituted derivatives (Scheme 1). 

Functional Macromolecules with Electron-Donating Dithiafulvene Unit... 

In this review, the recent progresses of functional macromolecules comprised with the dithiafulvene moiety, e.g., dithiafulvene/ -conjugated polymer hybrid systems, dendritic dithiafulvenes, polyrotaxane structures, and intramolecular CTs are highlighted. 

A series of -conjugated poly(dithiafulvene)s (12) have been prepared by cycloaddition polymerization of aldothioketenes and their alkynethiol tautomers, which were derived from aromatic diynes (Scheme 3) [70-73]. Efficient expansions of -conjugation systems in the polymers were evident... 

Poly(dithiafulvene)s toward intelligent functional materials have been synthesized [76-78]. An alternating -conjugated copolymer (13) of ferrocene with dithiafulvene showed a unique redox property [76]. Although 13... 

Fully conjugated side-chain dithiafulvene polymers have been also prepared [83, 84]. Polymerization of 2-ethynyl-TTF by use of a rhodium catalyst... 

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