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Although pristine tetrathiafulvalene (TTF) was firstly reported while TTF+ exhibits a planar D2h symmetry, TTF2+ is not planar
by Wudl in 19701 and, simultaneously and independently, by and has a D2 symmetry, whereas neutral TTF shows a slightly
Hünig et al.2 and Coffen et al.3 in 1971, the history of TTF boatlike structure with C2v symmetry.7
derivatives is considerably older. Actually, the dibenzo-fused The venture of TTF as a versatile strong electron donor
TTF4 was synthesized in the 1920s and dimethyl-TTF and molecule of interest for the preparation of electrically conduct-
diphenyl-TTF derivatives were reported in the 1960s.5 However, ing materials has its origin in the 1.5 pages pioneering Chemical
great interest in these sulfur-containing molecules started in Communications paper entitled: ‘‘Bis-1,3-dithiolium Chloride: an
the early 1970s, following the seminal paper of Wudl, when Unusually Stable Organic Radical Cation’’ by Wudl et al.1 In this
unsubstituted TTF arose as an electron donor with outstanding paper, pristine TTF was synthesized for the first time in a single
redox properties. step by deprotonation of 1,3-dithiolium hydrogen sulphate to
Since then, TTF and its derivatives have probably become the afford TTF in ca. 50% yield. Although compounds containing the
most famous electron donor molecules with over ten thousand TTF core had been prepared before, the properties of the parent
papers published in the scientific literature on the synthesis, compound TTF were not described. TTF was firstly described as
properties and applications of these singular molecules.6 a yellow solid; m.p. 118.5–1191, subl. 1001/0.3 mm; UV CH2C12,
Tetrathiafulvalene is a non-aromatic 14-p-electron system in lmax (e) 290 (4 104), 310 (4 104), and 365 (sh); i.r. (CH2Cl2,
which oxidation to the radical cation and dication states occurs mm) 7–95 (w), 12.55 (m), 12.8 (m), 13.6 (w), 15.5 (sh), and 15.9 (s);
sequentially and reversibly at relatively low oxidation potential NMR (CDCl3, d rel. to SiMe4) 5.68 (s);8 mass spectrum (70 eV),
values (E1/21 = 0.37 V and E1/22 = 0.67 V in dichloromethane vs. m/z 204 (100%, parent peak), strong peaks at m/z 159, 146, 102
the saturated calomel electrode) (Scheme 1). In contrast to the (100%, dication of parent), 88, and 76 (CS2). Furthermore, the
neutral TTF molecule, both the radical cation and dication most significant property of TTF is also stated in this manu-
species are aromatic in the Hückel sense due to the 6p-electron script. It was reported that TTF is readily photo-oxidized in the
heteroaromaticity of the 1,3-dithiolium cation and, therefore, presence of air to a violet, water-soluble substance presumed to
be a radical cation. The bisdithiole (TTF) reacts with electron
deficient olefins such as tetracyanoethylene, dichlorodicyano-
benzoquinone, etc. in analogy to other electron-rich olefins
(Scheme 2).9
Most importantly, in this communication the radical cation
(TTF+ Cl ) was prepared efficiently by the action of chlorine gas
on a carbon tetrachloride solution of TTF. It was also pointed
Scheme 1 TTF and its radical cation and dication species and their geometries
out that a stoichiometric amount of chlorine must be employed
calculated at the B3P86/6-31G** level.
a
Departamento de Quı́mica Orgánica, Facultad de Ciencias Quı́micas, Universidad
Complutense de Madrid, Ciudad Universitaria s/n, 28040 Madrid, Spain.
E-mail: nazmar@quim.ucm.es; Fax: +34 91-394-4103; Tel: +34 91-394-4227
b
Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA-Nanociencia),
Cantoblanco, 28049 Madrid, Spain Scheme 2 Synthesis of TTF and its oxidation to the radical cation.
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Fig. 3 Molecular rectifier proposed by Aviram and Ratner. Notes and references
Published on 13 June 2013. Downloaded by Universidade Federal de Mato Grosso on 10/1/2018 3:19:41 PM.
This journal is c The Royal Society of Chemistry 2013 Chem. Commun., 2013, 49, 7025--7027 7027