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Tetrathiafulvalene: the advent of organic metals

Cite this: Chem. Commun., 2013,
49, 7025
Received 10th January 2013,
Accepted 12th June 2013
DOI: 10.1039/c3cc00240c
Nazario Martı́n*ab
Tetrathiafulvalene (TTF) is among the most versatile and well-known molecules which exhibits outstanding
redox properties and a remarkable electron donor character. Its first synthesis was published in a short
communication by Wudl in 1970. In this viewpoint, its synthesis and characterization are discussed and,
most importantly, the significance of TTF in the development of electrically conducting materials (organic or
synthetic metals) and its further application in molecular electronics are highlighted.

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Although pristine tetrathiafulvalene (TTF) was firstly reported
by Wudl in 19701 and, simultaneously and independently, by
Hünig et al.2 and Coffen et al.3 in 1971, the history of TTF
derivatives is considerably older. Actually, the dibenzo-fused
TTF4 was synthesized in the 1920s and dimethyl-TTF and
diphenyl-TTF derivatives were reported in the 1960s.5 However,
great interest in these sulfur-containing molecules started in
the early 1970s, following the seminal paper of Wudl, when
unsubstituted TTF arose as an electron donor with outstanding
redox properties.
Since then, TTF and its derivatives have probably become the
most famous electron donor molecules with over ten thousand
papers published in the scientific literature on the synthesis,
properties and applications of these singular molecules.6
Tetrathiafulvalene is a non-aromatic 14-p-electron system in
which oxidation to the radical cation and dication states occurs
sequentially and reversibly at relatively low oxidation potential
values (E1/21 = 0.37 V and E1/22 = 0.67 V in dichloromethane vs.
the saturated calomel electrode) (Scheme 1). In contrast to the
neutral TTF molecule, both the radical cation and dication
species are aromatic in the Hückel sense due to the 6p-electron
heteroaromaticity of the 1,3-dithiolium cation and, therefore,
Scheme 1 TTF and its radical cation and dication species and their geometries
calculated at the B3P86/6-31G** level.
while TTF+ exhibits a planar D2h symmetry, TTF2+ is not planar
and has a D2 symmetry, whereas neutral TTF shows a slightly
boatlike structure with C2v symmetry.7
The venture of TTF as a versatile strong electron donor
molecule of interest for the preparation of electrically conduct-
ing materials has its origin in the 1.5 pages pioneering Chemical
Communications paper entitled: ‘‘Bis-1,3-dithiolium Chloride: an
Unusually Stable Organic Radical Cation’’ by Wudl et al.1 In this
paper, pristine TTF was synthesized for the first time in a single
step by deprotonation of 1,3-dithiolium hydrogen sulphate to
afford TTF in ca. 50% yield. Although compounds containing the
TTF core had been prepared before, the properties of the parent
compound TTF were not described. TTF was firstly described as
a yellow solid; m.p. 118.5–1191, subl. 1001/0.3 mm; UV CH2C12,
lmax (e) 290 (4  104), 310 (4  104), and 365 (sh); i.r. (CH2Cl2,
mm) 7–95 (w), 12.55 (m), 12.8 (m), 13.6 (w), 15.5 (sh), and 15.9 (s);
NMR (CDCl3, d rel. to SiMe4) 5.68 (s);8 mass spectrum (70 eV),
m/z 204 (100%, parent peak), strong peaks at m/z 159, 146, 102
(100%, dication of parent), 88, and 76 (CS2). Furthermore, the
most significant property of TTF is also stated in this manu-
script. It was reported that TTF is readily photo-oxidized in the
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
out that a stoichiometric amount of chlorine must be employed

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.

This journal is c The Royal Society of Chemistry 2013 Chem. Commun., 2013, 49, 7025--7027 7025

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to avoid further oxidation to the yellow dication (TTF2+). Inter-

estingly, the ESR spectrum of the radical cation (TTF+ Cl )
(H2O–MeCN, 25 1C or EtOH, 50 1C) is a quintet, indicating
four equivalent protons; aH = 1.26  0.02, g = 2.00838.
Finally, in this work the redox reversibility of the radical

cation species (TTF+ ) was also discussed provided that chemical
reduction with sodium hydrogen bisulphite allowed recovering
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the neutral species (TTF).
Soon afterwards, the discovery of the first organic conduc-

tors based on tetrathiafulvalene (TTF+ Cl ) in 1972 (ref. 10) and
metal TTF–TCNQ in 1973 (ref. 11) made tetrathiafulvalene one
of the most studied and well-known heterocyclic systems, and
one of the most important molecular building blocks for the
development of the so-called electrically conducting materials
(also known as organic metals or synthetic metals) as well as the
further and challenging development of molecular electronics.
TTF stacks in the solid state when combined with p-electron
acceptors to form charge transfer complexes (CTCs). Many of
the so formed CTCs possess interesting conducting and mag-
netic properties. The most famous and relevant CTC, being the
first organic metal, was formed by TTF and the strong electron
acceptor 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) with a
1 : 1 stoichiometry (Fig. 1). The electrical conductivity deter-
mined for this CTC showed typical metallic behaviour at
T > 54 K. Interestingly, TTF and TCNQ molecules form segre-
gated molecular stacks in the complex, resulting in strongly
anisotropic conducting properties, with a Peierls transition
(from metal to insulator) at lower temperature (T o 54 K).
Just a few years ago a most intriguing finding was reported:
when placed next to each other, the crystals of TTF and TCNQ
stick together and, surprisingly, form a conducting strip about
2 nm across at their interface. The current flows between the
surfaces and is confined to the two layers of molecules in
contact, which requires high quality surfaces (Fig. 2).12
The excitement aroused in the scientific community by the
realization that organic compounds were able to conduct
electricity, similarly to metals, led to a huge synthetic effort
for the preparation of new TTF derivatives, namely by modifying
the substitution pattern at the periphery of the molecule or by
replacing the S atom by a different calcogen (Se, Te).13
A breakthrough in the field of electrically conducting mate-
rials was the use of the tetraselenafulvalene (TSF) derivative
tetramethyl-TSF (TMTSF) which led to the first organic
Fig. 1 Segregated stacks of TTF and TCNQ (from CCDC).
7026 Chem. Commun., 2013, 49, 7025--7027
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Fig. 2 Crystals of TTF (yellow) and TCNQ (red) (from ref. 12).
superconductors (Tc = 1–2 K) of formula (TMTSF)2X (X = PF6 ,
AsF6 , TaF6 , NbF6 , ReO4 and ClO4 ) firstly reported by
Bechgaard in 1980 (ref. 14) and, since then, known as
Bechgaard’s salts.
Interestingly, only the perchlorate salt resulted to be a
superconductor at ambient pressure, whereas the others
required the application of high pressure (5–12 kbar) to the
crystals to get superconducting properties. X-Ray structure
determination showed that the ClO4 anions are located within
channels in the stacked structure with short and stabilizing
O


H contacts.
Since then, and during the last three decades, a great variety
of new tetrachalcogenofulvalene-based superconductors have
been synthesised, thus improving the field of electrically con-
ducting materials. Among them, the most relevant have been
the salts of bis-ethylenedithio-tetrathiafulvalene (BEDT-TTF) of
formula (BEDT-TTF)2X which showed superconducting behav-
ior at Tc = 11.6 K in k-(BEDTTTF)2[Cu(CN)2]Br (ref. 15) and
Tc = 12.8 K in k-(BEDT-TTF)2[Cu(CN)2]Cl under an applied
pressure of 0.3 kbar.16
The chemical structures of these salts are organized in a
kappa-packing motif of orthogonal dimers of BEDT-TTF molec-
ules and a chain network of the respective anions. Therefore,
they are structurally different from the planar stacks of TTF or
TMTSF units found in the aforementioned TTF–TCNQ complex
or (TMTSF)2X salts. So far, all attempts carried out to improve
the critical temperature Tc by modifying the BEDT-TTF molec-
ule, either by using O or Se atoms or by changing the substitu-
tion pattern at the periphery, have been unsuccessful. The
increase of Tc for the phase transition into the superconducting
state in organic materials has only been achieved more recently
in doped cubic and hexagonal C60 fullerene crystals (namely
with alkaline and alkaline-earth metals) such as RbTl2C60
which exhibits one of the highest values of the Tc of 48 K
reported so far.17
Despite the above important scientific findings, which
would be more than enough for a molecule to be considered
at the top in chemistry, TTF and its derivatives offer new and in
some cases little-exploited possibilities at the molecular,
macromolecular and supramolecular levels. Actually, the inter-
est in the TTF molecule goes beyond the field of materials
chemistry and, in this regard, in addition to the covalent
This journal is c The Royal Society of Chemistry 2013

ChemComm
Fig. 3 Molecular rectifier proposed by Aviram and Ratner.
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chemistry, TTF is an important building block in supramolec-
ular chemistry, crystal engineering, and in systems able to
operate as machines.6 Furthermore, TTF has been used as a
catalyst for radical-polar crossover reactions, thus mimicking
the samarium iodide chemistry.18
Actually, in recent years, a variety of new concepts have been
applied to TTF and its derivatives. Thus, chemical sensors and
redox-switchable ligands have been prepared from TTF while
molecular shuttles, molecular switches and logic gates have
been prepared from TTF-containing rotaxanes and catenanes.19
A large synthetic effort has been devoted to the preparation of
the so-called organic ferromagnets, many of which are derived
from TTF.6
TTF has also played a prominent role in molecular electronics.
Since 1974, when Aviram and Ratner proposed in a theoretical
paper that rectification of electrical current through a single
Donor–spacer–Acceptor (D–s–A) molecule could be possible
(Fig. 3),20 a great synthetic effort has been undertaken to prepare
a variety of molecules in which a strong donor moiety is
covalently attached to a strong acceptor moiety through a
covalent, saturated bridge. Eventually, this concept became a
reality when new D–s–A molecules allowed the preparation of the
first confirmed unimolecular rectifier.21
It has also been confirmed that TTF can display efficient
nonlinear optic (NLO) responses in the second and third
harmonic generation as well as a good thermal stability. These
findings can be combined with the redox ability of TTF as an
external stimulus to provide a promising strategy for the
molecular engineering of switchable NLO materials.22
The design and synthesis of organic molecules with two
photo and redox chromophores, namely an electroactive donor
and an acceptor fragment connected through a spacer, that
display photoinduced charge separation is an important topic
in chemistry. These molecules can be used as artificial photo-
synthetic systems to transform sunlight into chemical energy.
In this regard, fullerenes have been shown to have unique
photophysical properties for the preparation of photovoltaic
devices.23 The first fullerene endowed with TTF was reported in
1996 showing remarkable photophysical properties and leading
to photoinduced charge-separated (CS) states with remarkable
lifetimes. Since then, a wide variety of C60-TTF have been
prepared. In contrast to other known electron donor molecules,
TTF and its derivatives are non-aromatic molecules which upon
oxidation form the 1,3-dithiolium cation which possesses
aromatic character (Scheme 1). This gain of aromaticity in
forming the radical cation and dication species of TTF in the
oxidation process is an important improvement for increasing
the stabilization of the charge-separated state in the search for
efficient photovoltaic systems.24
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In summary, this pioneering work by Wudl with 248 cita-
tions (Scifinder) represents one of the important and outstand-
ing landmarks in chemistry. As a result, TTF and its derivatives
have gained a prominent place in science in their own right.
Notes and references
1 F. Wudl, G. M. Smith and E. J. Hufnagel, J. Chem. Soc., Chem.
Commun., 1970, 1453–1454.
2 S. Hünig, G. Kiesslich, D. Sceutzow, R. Zhrandik and P. Carsky, Int. J.
Sulfur Chem., Part C, 1971, 109–122.
3 D. L. Coffen, J. Q. Chambers, D. R. Williams, P. E. Garrett and
N. D. Canfield, J. Am. Chem. Soc., 1971, 93, 2258–2269.
4 W. R. H. Hurtley and S. Smiles, J. Chem. Soc., 1926, 2263–2270.
5 H. Prinzbach, H. Berger and A. Lüttringhaus, Angew. Chem., Int. Ed.
Engl., 1965, 4, 435–439.
6 Many review papers have been devoted to TTF and its derivatives.
Just to name a few published in the last few years, see:
(a) M. R. Bryce, J. Mater. Chem., 2000, 10, 589–598; (b) J. L. Segura
and N. Martı́n, Angew. Chem., Int. Ed., 2001, 40, 1372–1409;
(c) M. Bendikov, F. Wudl and D. F. Perepichka, Chem. Rev., 2004,
104, 4891–4945. See also: (d) P. Batail (Ed.), Special issue on
Molecular Conductors, Chem. Rev., 2004, 104, 4887–5781.
7 (a) C. Katan, J. Phys. Chem. A, 1999, 103, 1407–1413; (b) I. Hargittai,
J. Brunvoll, M. Kolonits and V. Khodorkovsky, J. Mol. Struct., 1994,
317, 273–277.
8 The proton resonance of TTF2+ is downfield-shifted to 9.51 ppm;
P. R. Ashton, V. Balzani, J. Becher, A. Credi, M. C. T. Fyfe,
G. Mattersteig, S. Menzer, M. B. Nielsen, F. M. Raymo, J. F. Stoddart,
M. Venturi and D. J. Williams, J. Am. Chem. Soc., 1999, 121, 3951–3957.
9 (a) N. Wiberg, Angew. Chem., Int. Ed. Engl., 1968, 7, 766;
(b) R. W. Hoffmann, Angew. Chem., Int. Ed. Engl., 1968, 7, 754–765.
10 F. Wudl, D. Wobschall and E. J. Hufnagel, J. Am. Chem. Soc., 1972,
94, 670–672.
11 J. Ferraris, D. O. Cowan, V. V. Walatka Jr. and J. H. Perlstein, J. Am.
Chem. Soc., 1973, 95, 948–949.
12 H. Alves, A. S. Molinari, H. Xie and A. F. Morpurgo, Nature Mater.,
2008, 7, 574–580.
13 (a) M. R. Bryce, J. Mater. Chem., 1995, 5, 1481–1496; (b) G. Schukat
and E. Fanghänel, Sulfur Rep., 1996, 18, 1–12; (c) J. Garı́n, Adv.
Heterocycl. Chem., 1995, 62, 249–304.
14 K. Bechgaard, C. S. Jacobsen, K. Mortensen, H. J. Pederson and
N. Thorup, Solid State Commun., 1980, 33, 1119–1125.
15 A. M. Kini, U. Geiser, H. Wang, K. D. Carlson, J. M. Williams,
W. K. Kwok, K. G. Vandervoot, J. E. Thompson, D. L. Stupka, D. Jung
and M.-H. Whangbo, Inorg. Chem., 1990, 29, 2555–2557.
16 J. M. Williams, A. M. Kini, H. Wang, K. D. Carlson, U. Geiser,
L. K. Montgomery, G. J. Pyrka, D. M. Watkins, J. M. Kommers,
S. J. Oryschuk, A. V. Striebycrouch, W. K. Kwok, J. E. Schirber,
D. L. Overmeyer, D. Jung and M.-H. Whangbo, Inorg. Chem., 1990,
29, 3262–3265.
17 V. M. Loktev, É. A. Pashitskiı̄, R. Shekhter and M. Jonson, Low Temp.
Phys., 2002, 28, 821–829.
18 (a) J. A. Murphy and S. J. Roome, J. Chem. Soc. Perkin Trans. 1, 1995,
1349–1353; (b) L. F. Tietze and U. Beifuss, Angew. Chem., Int. Ed.
Engl., 1993, 32, 131–163.
19 C. P. Collier, E. W. Wong, M. Belohradsky, F. M. Raymo, J. F. Stoddart,
P. J. Kuekes, R. S. Williams and J. R. Heath, Science, 1999, 285, 391–394.
20 A. Aviram and M. Ratner, Chem. Phys. Lett., 1974, 9, 2271–2275.
21 R. M. Metzger, B. Chen, U. Höpfner, M. V. Lakshmikantham,
D. Villaume, T. Kawai, X. Wu, H. Tachibana, T. V. Hughes,
H. Sakurai, J. W. Baldwin, C. Hosch, M. P. Cava, L. Brehmer and
G. J. Ashwell, J. Am. Chem. Soc., 1997, 119, 10455–10466.
22 (a) A. I. de Lucas, N. Martı́n, L. Sánchez, C. Seoane, R. Andreu,
J. Garı́n, J. Orduna, R. Alcalá and B. Villacampa, Tetrahedron, 1998,
54, 4655; (b) M. González, J. L. Segura, C. Seoane, N. Martı́n, J. Garı́n,
J. Orduna, B. Villacampa, R. Alcalá, V. Hernández and J. T. López-
Navarrete, J. Org. Chem., 2001, 66, 8872–8882.
23 J. L. Delgado, P. A. Bouit, S. Filippone, M. A. Herranz and N. Martin,
Chem. Commun., 2010, 46, 4853–4865.
24 (a) N. Martı́n, L. Sánchez, M. A. Herranz, B. Illescas and D. M. Guldi,
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Chem. Commun., 2013, 49, 7025--7027 7027