Inorganica Chimica Acta 360 (2007) 3909–3914

www.elsevier.com/locate/ica

Synthesis and characterization of the novel extended TTF-type

donors with thiophenic units
D. Belo a, M.J. Figueira a, J.P.M. Nunes a, I.C. Santos a, M. Almeida a,*
,
N. Crivillers b,1, C. Rovira b,1
a
Dept. Quı́mica, Instituto Tecnológico e Nuclear/CFMCUL, P-2686-953 Sacavém, Portugal
b
Institut de Ciència de Materials de Barcelona (CSIC), Campus Universitari de Bellaterra, E-08193 Cerdanyola, Spain

Received 27 November 2006; received in revised form 16 March 2007; accepted 24 March 2007
Available online 30 March 2007

Paper presented in the MAGMANet-ECMM, European Conference on Molecular Magnetism, that took place last October 10–15 in Tomar, Portugal.

Abstract

Two new TTF-based donors that are dithiolene ligand precursors, 3-{5-[(2-cyanoethyl)thio]-2-(5,6-dihydrothieno[2,3-d][1,3]dithiol-2-
ylidene-1,3-dithiol-4-yl)thio}propanenitrile, dtdt (1) and 3-({5-[(2-cyanoethyl)thio]-2-thieno[2,3-d][1,3]dithiol-2-ylidene-1,3-dithiol-4-
yl)thio}propanenitrile, a-tdt (2), were synthesized and characterized. The electrochemical properties of these compounds were studied
by cyclic voltammetry (CV) in acetonitrile. Compound 1 shows two reversible oxidation process at 1E1/2 = 0.639 V and 2E1/2 =
0.997 V versus Ag/AgCl. This same processes occurs at 1E1/2 = 0.612 V and 2E1/2 = 0.906 V in the case of 2. The crystal structures con-
firm the ability of these molecules to establish interactions with their neighbours through the peripheral sulfur atoms.
 2007 Elsevier B.V. All rights reserved.

Keywords: Synthesis; Cyclic voltammetry; Thiophene; Extended TTF

1. Introduction increasing number of sulfur atoms in the periphery, which

can play a significant role in reducing the on-site Coulom-
The TTF molecule, due to its unique p-donor properties, bic repulsion and increasing the strength and dimensional-
has been at the basis of many charge transfer salts with ity of solid state interactions due to more S


S contacts.
unique electronic and magnetic properties since its prepara- Indeed one of the most successful TTF derivatives is the
tion [1] and the discovery of first organic conductors [2], [bis(ethylenedithio)tetrathiofulvalene], BEDT-TTF, which
more than 30 years ago. Its ability to form partially oxi- leads to an enormous number of radical-ion salts, showing
dized states gave rise to many molecular conductors [3], a rich diversity of electronic behaviour, including circa 100
and in fact the large majority of organic metals and super- superconductors [4].
conductors known so far are based on TTF derivatives. Following a similar approach, a series of donors based
One of the trends in the preparation of new TTF deriva- on TTF fused with thiophene moieties have also been
tives for electronic materials is the search for molecules explored leading to charge transfer salts with unique prop-
with, simultaneously, more extended p-systems and an erties [5].
More recently, some extended TTF-based ligands were
also used in the preparation of transition metal bisdithio-
*
lates obtained from cyanoethyl substituted TTF-dithio-
Corresponding author. Tel.: +351 219946171; fax: +351 219941455.
E-mail addresses: [email protected] (M. Almeida), [email protected] (N.
lates. One of the most interesting compounds obtained
Crivillers), [email protected] (C. Rovira). from these extended TTF dithiolene ligands, so far, is the
1
Tel.: +344 93 5801853; fax: +344 93 5805729. neutral complex Ni(tmdt)2, which at room temperature

0020-1693/$ - see front matter  2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2007.03.041
3910 D. Belo et al. / Inorganica Chimica Acta 360 (2007) 3909–3914

displays an electrical conductivity of 400 S/cm and trans-

port properties typical of a metallic system [6].
In this paper, we report the synthesis and characteriza-
tion of two new sulfur rich TTF-type donors fused with
thiophene moieties, 3-{5-[(2-cyanoethyl)thio]-2-(5,6-dihy-
drothieno[2,3-d][1,3]dithiol-2-ylidene-1,3-dithiol-4-yl)thio}-
propanenitrile, dtdt (1) and 3-({5-[(2-cyanoethyl)thio]-2-
thieno[2,3-d][1,3]dithiol-2-ylidene-1,3-dithiol-4-yl)thio}pro-
panenitrile, a-tdt (2), which are also precursors for the
preparation of new extended thiophene-TTF fused dithio-
lene ligands.

2. Results and discussion

The preparation of the novel asymmetric TTF donors

fused with thiophene moieties 1 and 2 was achieved
following a synthetic route first used by Underhill and
co-workers [7] involving the coupling with phosphorous Fig. 1. Cyclic voltamograms of dtdt (grey) and a-tdt (black).
methoxide between ketones I and II and thione III
(Scheme 1). The electrochemical studies of 1 and 2 show two quasi
Ketone I, 5,6-dihydrothieno[2,3-d]-1,3-dithiol-2-one was reversible single electron oxidation processes typical of
obtained, with low but reproducible yield, through a TTF-based donors (see Fig. 1). Cyclic voltammetry of
multi-step reaction previously described [8] and ketone II, a-tdt, in acetonitrile, shows a pair of asymmetric redox
5,6-thieno[2,3-d]-1,3-dithiol-2-one was obtained, in a quan- waves at (0.904, 1.090 V) 0.997 V versus Ag/AgCl, that
titative yield, by dehydrogenation of I using DDQ [9]. correspond to the couple [a-tdt]+/[a-tdt]2+. At lower
Thione III, 4,5-bis(2-cyanoethylthio)-1,3-dithiole-2-thione, potentials there is a pair of reversible waves centred at
was prepared as previously described [10] using bis- 0.639 V corresponding to the couple [a-tdt]0/[a-tdt]+.
(tetraethylammonium)bis(2-thioxo-1,3-dithiole-4,5-dithio- For dtdt, the reversible waves that correspond to the
late)zincate complex [11] as precursor, by a nucleophilic [dtdt]0/[dtdt]+ couple are observed at 0.612 V and a sec-
substitution reaction [7]. ond, reversible but asymmetric, pair of redox waves is
The coupling reaction of Scheme 1 leading to com- observed at (0.851, 0.962 V) 0.906 V that is ascribed to
pounds 1 and 2 also gives rise to several by-products result- the [dtdt]+/[dtdt]2+ couple. These same studies performed
ing mainly from the self-coupling of the reactants. using DMF as a solvent show the same oxidation pro-
However reasonable yields, 20% and 28% for 1 and 2, cesses, at slightly lower potentials. The asymmetric nature
respectively, were achieved after column purification, using of these last waves is typically due to the formation of a
dichloromethane as a solvent, and optimization of some less soluble product that precipitates on the electrode.
reaction parameters, such as temperature, reaction time These electrochemical studies show that the non-aromatic
or solvent amount, to cause the precipitation of the formed compound is slightly easier to oxidize than the aromatic
TTF compounds, which were found critical for the final one, indicating that the aromatic thiophenic ring in a-
yield and purity. These compounds are soluble in usual tdt stabilizes the neutral state. The redox potential values
organic solvents, such as dichloromethane and acetonitrile, obtained are comparable with those observed in the corre-
and single crystals suitable for RX measurements were sponding symmetric thiophenic-TTF-based donors, such
obtained from slowly cooling dichloromethane and satu- as bis(ethylenethio)tetrathiafulvalene (BET-TTF) and a-
rated n-hexane solutions. dithiophenetetrathiathiophene (a-DT-TTF), sharing in a

S CN
S S
S
O

S S S CN
S S CN S
S
S (I) P(OMe) 3 75º / 80º C (1) dtdt Yield 20 %
or + S
24h or
S CN
S
S
O S
(III) S S CN
S
S (II) S S S CN
S
(2) α -tdt Yield 28 %

Scheme 1.
 D. Belo et al. / Inorganica Chimica Acta 360 (2007) 3909–3914 3911

Table 1 and 2 (Table 1). From this comparison, we observe that

Electrochemical data of TTF derivatives 1 and 2 as well as of the related the asymmetric fusion of the TTF core with only one thi-
donors
ophenic ring reduces the donor properties compared both
1 2
Donor Solvent E1/2 (V) E1/2 (V) with simple TTF and with TTF bisfused derivatives, BET-
BET-TTF MeCN [13] 0.39 0.66 TTF and a-DT-TTF, but rises these donor properties
DMF [14] 0.43 0.58 when compared with TCNEt-TTF.
a-DT-TTF DMF [14] 0.50 0.67
TTF MeCN [15] 0.37 0.75
Compound 1 crystallizes in the orthorhombic system,
DMF [16] 0.39 0.62 space group Pca21, Z = 4, with unit cell parameters a =
(TCNEt-TTF)a DMF 0.64 0.84 30.463(6) Å, b = 9.0732(18) Å, c = 7.0201(14) Å. The unit
dtdt MeCN 0.61 0.91 cell contains one independent dtdt molecule in a general
DMF 0.53 0.72 position, which presents a slight boat type distortion of
a-tdt MeCN 0.64 1.00
DMF 0.56 0.73
the TTF core (Fig. 2). The terminal thiophenic sulfur
atom presents an orientational disorder with occupation
Potentials vs. Ag/AgCl; Pt working and counter electrodes.
a
2,3,6,7-Tetrakis(2-cyanoethylthio)TTF obtained as a by-product of the
factors of 75% and 25% for S1 and S1A, respectively.
synthesis reported in this work. The dihedral angle between the plane of the central core
of the molecule (defined by the S5, S4, C5, C6, S3, S2
atoms) and the thiophenic ring is 10.7, and between
the plane defined by the atoms C7, C8, S7, S6 in the
symmetrical fashion the same terminal thiophenic units opposite end is 10.2. The bond lengths of the molecule
and 2,3,6,7-tetrakis(2-cyanoethylthio)tetrathiafulvalene [12] are within the expected range of values for neutral TTF
(TCNEt-TTF), a TTF substitute with four cyanoethyl derivatives [17].
‘‘arms’’, obtained as by-product in the synthesis of 1 The crystal structure is composed by head to tail stacks
of dtdt molecules along b. These stacks are made of mole-
cules with their long axis in alternated orientations, making
an angle of circa 45 (Fig. 3b), and are interlocked in such a
way that the cyanoethyl ‘‘arms’’ are segregated from the
TTF cores in alternated layers parallel to the a, c plane
(Fig. 3a).
Molecules parallel to each other are connected by a
short S4


S7 contact (Fig. 3b, Table 2). Molecules with
their long axis tilted almost 45 (depicted in different shades

Fig. 2. ORTEP views and atomic numbering scheme of dtdt (1) with
thermal ellipsoids at 40% probability level. Fig. 3. Crystal structure of 1: (a) viewed along c and (b) viewed along b.
3912 D. Belo et al. / Inorganica Chimica Acta 360 (2007) 3909–3914

Table 2
Hydrogen bonds and short contacts in the crystal structure of compound 1
d (Å) Angle ()
S4


S7 3.687
N2


H10b–C10 2.673 136
N2


H9b–C9 2.519 154
N1


H13a–C13 2.588 141

Fig. 5. Crystal structure of 2: (a) viewed along a and (b) viewed along b.

of the –(CH2)2–CN ‘‘arms’’ which lie almost perpendicu-

Fig. 4. ORTEP views and atomic numbering scheme of a-tdt Æ CH2Cl2 (2) larly to the TTF core. Excluding these atoms, the atomic
with thermal ellipsoids at 40% probability level. deviations from the average TTF plane are less than
0.069 Å. As imposed by the crystal symmetry the molecule
presents 50% orientation disorder of the terminal thiophe-
in Fig. 3b) are connected by one short S


S contact nic ring. The bond lengths of the molecule are within the
(3.71 Å apart, only slightly above the S–S van der Walls expected range typical of neutral TTF [17].
radii sum). Some C–H


N hydrogen bonds are also bridg- The crystal structure consists of stacks along a of tdt
ing these two kinds of molecules (Table 2). molecules tilted toward this axis so that the angle between
Along a the closest layers are connected by several a and the normal of the TTF plane is 36.2. The unit cell
C–H


N hydrogen bonds, involving the cyanoethyl contains two stacks with parallel TTF planes but with
‘‘arms’’ (Table 2). opposite tail orientations. Again, as in the previous struc-
Compound 2 crystallizes in the monoclinic system, space ture, there is a significant segregation of cyanoethyl groups
group P21/m, Z = 2, with unit cell parameters and solvent molecules from the TTF cores in layers alter-
a = 5.9780(13) Å, b = 12.387(3) Å, c = 13.933(3) Å and nating along c (Fig. 5).
b = 96.059(4). The unit cell contains one independent tdt The overlap mode between molecules in a column is that
molecule, positioned in a mirror plane containing C3 and of the thiophenic ring over TTF ring, with an interplanar
C4 and perpendicular to the central TTF core, and one distance of 3.53 Å and with a shortest S


S distance of
independent dichloromethane molecule also in a mirror 3.798 Å, slightly larger than the van der Walls radii sum.
plane (Fig. 4). The tdt molecule is planar with the exception The molecules in the neighbouring columns interact
 D. Belo et al. / Inorganica Chimica Acta 360 (2007) 3909–3914 3913

Table 3 The measurements were performed at room temperature

Hydrogen bonds and short contacts in the crystal structure of compound 2 in acetonitrile and dimethylformamide that contained
d (Å) Angle () n-Bu4PF6 (10 1 M) as the supporting electrolyte, with a
S4


S1 3.618 scan rate of 100 mV/s, platinum wire working and counter
S3


S2 3.621 electrodes and a Ag/AgCl reference electrode.
N1


H9a–C9 2.352 149
Cl


H1–C1 2.763 134
4.2. Synthesis

through side-by-side S


S short contacts (Fig. 5a, Table 3). 4.2.1. 3-{5-[(2-Cyanoethyl)thio]-2-(5,6-dihydrothieno[2,3-
There are also several hydrogen bonds of the C–H


Cl and d][1,3]dithiol-2-ylidene-1,3-dithiol-4-yl)thio}
C–H


N type, between a-tdt and dichloromethane (Table propanenitrile, dtdt (1)
3). Compound I (1.223 g, 6.94 mmol) and compound III
These multi-sulfurated molecules tend to position them- (2.2 g, 7.22 mmol) were dissolved in 12 mL of P(OMe)3 in
selves, side-by-side, in order to maximize the sulfur–sulfur a 50 mL round bottomed flask. The mixture is heated to
interactions. 75 C/80 C for 24 h. Upon cooling, 60 mL of methanol
was added and the mixture was cooled down to 15 C,
3. Conclusions during 24 h. The precipitate was filtered off and washed
with 3 · 10 mL of methanol and dried under vacuum. This
The convenient synthesis of two new TTF-based donors solid was purified by column chromatography, using
fused with thiophene moieties and substituted with dithio- CH2Cl2 as a solvent (rf = 0.35). Single crystals, suitable
lene precursors, 3-{5-[(2-cyanoethyl)thio]-2-(5,6-dihydro- for RX measurements were obtained from cooling down
thieno[2,3-d][1,3]dithiol-2-ylidene-1,3-dithiol-4-yl)thio}pro- a refluxed 3:1 n-hexane/CH2Cl2 solution. Yield 20%
panenitrile, dtdt (1) and 3-({5-[(2-cyanoethyl)thio]-2- (592 mg); Elemental Anal. Calc. for C14H12N2S7: C,
thieno[2,3-d][1,3]dithiol-2-ylidene-1,3-dithiol-4-yl)thio}pro- 38.86; H, 2.80; N, 6.47; S, 51.87. Found: C, 39.49; H,
panenitrile, a-tdt (2), was achieved. These new molecules 2.51; N, 6.23; S, 51.35%. FT-IR (KBr), cm 1: 2925 (m,
show reduced donor properties when compared with the –CH2–), 2253 (m, AC„N), 1617 and 1482 (m, C@C),
corresponding symmetrically thiophene fused TTFs. As 1425 (S, S–CH2–R); H NMR (300 MHz, CDCl3):
sulfur rich molecules they display a crystal structure dom- d = 3.781 (t, J = 8 Hz, 2H, –C2H2–C1H2–S1–); 3.084 (t,
inated by several short S


S contacts. These TTF donors J = 7 Hz, 2H, –C4–C2H2 Æ C1H2–); 2.876 (t, J = 8 Hz,
are also ligand precursors for preparing bisdithiolene com- 4H, S–CH2–CH2–CN); 2.738 (t, J = 7 Hz, 4H, S–CH2–
plexes with highly extended ligands, currently under study CH2–CN) ppm; MS: m/z (%) = 431.9 (M+,100); M.p.:
in our laboratory, and which will be reported in due course. 129–130 C.

4. Experimental 4.2.2. 3-({5-[(2-Cyanoethyl)thio]-2-thieno[2,3-

d][1,3]dithiol-2-ylidene-1,3-dithiol-4-yl}thio)propane-
4.1. General nitrile, a-tdt (2)
This compound was prepared by using the same method
All solvents were purified following standard proce- described for 1, using precursor II instead of precursor I.
dures. 4,5-bis(2-cyanoethylthio)-1,3-dithiole-2-thione (III) The solid obtained was purified by column chromatogra-
and bis(tetraethylammonium)bis(2-thioxo-1,3-dithiole-4,5- phy with CH2Cl2 as a solvent (rf = 0.35). Single crystals
dithiolate) zincate complex were prepared by an analogous suitable for RX measurements, were obtained from slowly
procedure to that in Refs. [10,11] above, 5,6-dihydrothi- cooled 3:1 n-hexane/CH2Cl2 solutions. Yield 28% (743
eno[2,3-d]-1,3-dithiol-2-one (I) and 5,6-thieno[2,3-d]-1,3- mg); Elemental Anal. Calc. for C14H10N2S7: C, 39.04; H,
dithiol-2-one (II) were synthesized as previously described 2.34; N, 6.50; S, 52.12. Found: C, 39.65; H, 2.34; N, 6.47;
[8,9]. Other chemicals were commercially obtained and S, 53.06%. FT-IR (KBr), cm 1: 3077 (w, AC„N), 2926
used without further purification. Column chromatogra- (m, –CH2–), 2250 (m, AC„N), 1634 and 1487 (w,
phy was carried out using silica gel (0.063 ± 0.2 mm) from AC@CA), 1416 (s, S–CH2–R); H NMR (250 MHz,
SDS. IR spectra were obtained on a Perkin–Elmer 577 CDCl3): d = 7.30 (d, J = 5 Hz, 2H, –C10H–C1H–S1–);
spectrophotometer. 1H NMR spectra were recorded on a 6.84 (d, J = 5 Hz, 2H, –C1H–C10H–C2–); 3.11 (t,
Brucker Aspect 3000 (300 MHz for 1H) and CDCl3 was J = 7 Hz, 4H, –S4–C6H2–C7H2–CN); 2.74 (t, J = 7 Hz,
used as the solvent, TMS was the internal reference. 4H, –S4–C6H2–C7H2–CN) ppm; MS: m/z (%) = 429.7
MALDI mass spectra were obtained in time-of-flight nega- (M+,100); M.p.: 137–138 C.
tive linear mode on a Kratus Kompact Maldi 2K probe
(KRATOS Analytical) that was operated with pulsed 5. X-ray crystallographic study
extraction of the ions. Cyclic voltammetry data were
obtained using a EG&G PAR 263A potentiostat galvano- X-ray diffraction experiments were performed with a
stat with a cell equipped with a double KCl (3 M) bridge. Bruker AXS APEX CCD detector diffractometer using grap-
3914 D. Belo et al. / Inorganica Chimica Acta 360 (2007) 3909–3914

Table 4 [email protected]. Supplementary data associated with

Crystallographic data and structure refinement results for dtdt (1) and this article can be found, in the online version, at
a-tdt Æ CH2Cl2 (2 Æ CH2Cl2)
doi:10.1016/j.ica.2007.03.041.
Formula C14H12N2S7 (1) C15H12Cl2N2S7
(2 Æ CH2Cl2)
Molecular weight 432.68 430.66 References
Crystal system orthorhombic monoclinic
Space group Pca21 P21/m [1] F. Wudl, G.M. Smith, E.J. Hufnagel, J. Chem. Soc., Chem. Commun.
T (K) 295(2) 130(2) 1453 (1970).
a (Å) 30.453(6) 5.9780(10) [2] (a) F. Wudl, D. Wobschall, E. Hufnagel, J. Am. Chem. Soc. 94 (1972)
b (Å) 9.0732(18) 12.387(2) 670;
c (Å) 7.0201(14) 13.933(2) (b) J. Ferraris, D.O. Cowan, V.V. Walatka Jr., J.H. Perlstein, J. Am.
b () 96.059(3) Chem. Soc. 95 (1973) 948.
V (Å3) 1939.7(7) 515.59 [3] (a) Special issue on molecular conductors, Chem. Rev. 104(11)
Z 4 2 (2004);
k (Å) 0.71073 0.71073 (b) J. Yamada, T. Sugimoto, TTF Chemistry Fundamentals and
l (Mo Ka) (mm 1) 0.811 1.033 Applications of Tetrathiafulvalene, Springer-Verlag, Berlin, 2004.
Crystal size (mm) 0.22 · 0.16 · 0.06 0.35 · 0.25 · 0.02 [4] (a) J.M. Williams, J.R. Ferraro, R.J. Thorn, K.D. Carlson, U. Geiser,
hmax () 23.42 27.10 H.H. Wang, A.M. Kini, M.-H. Whangbo, Organic Superconductors
Tmin, Tmax 0.8418/0.9530 0.7138/0.9796 (Including Fullerenes) Synthesis, Structure, Properties, and Theory,
Measured reflections 4534 4161 Prentice Hall, Englewood Cliffs, NJ, 1992;
Independent reflections 2568 2360 (b) J.-P. Farges, Organic Conductors Fundamentals and Applica-
Rint 0.0436 0.0475 tions, Marcel-Dekker Inc., New York, 1994;
Data/restraints/ 2568/21/223 2360/8/153 (c) T. Ishiguro, K. Yamaji, G. Saito, Organic Superconductors,
parameters Springer-Verlag, New York, 1998.
R(F2)[F2 > r(F2)] 0.0460 0.0490 [5] C. Rovira, Chem. Rev. 104 (2004) 5289.
wR(F2) 0.0785 0.0907 [6] H. Tanaka, Y. Okano, H. Kobayashi, W. Suzuki, A. Kobayashi,
Science 291 (2001) 285.
[7] (a) N.L. Narvor, N. Robertson, A.E. Underhill, et al., J. Chem. Soc.,
hite monochromated Mo Ka radiation (k = 0.71073 Å), in Chem. Commun. (1996) 1363;
the u and x scans mode. A semi empirical absorption cor- (b) N.L. Narvor, N. Robertson, A.E. Underhill, et al., J. Chem. Soc.,
rection was carried out using SADABS [18]. Data collection, Dalton Trans. (1996) 823.
[8] A. Pérez-Benı́tez, J. Tarrés, E. Ribera, J. Veciana, C. Rovira,
cell refinement and data reduction were done with the
Synthesis 4 (1999) 577.
SMART and SAINT programs [19]. The structures were solved
[9] D. Belo, H. Alves, E.B. Lopes, M.T. Duarte, V. Gama, R.T.
by direct methods using SIR97 [20] and refined by full- Henriques, M. Almeida, A. Pérez-Benı́tez, C. Rovira, J. Veciana,
matrix least-squares methods using the program SHELXL97 Chem. Eur. J. 7 (2001) 511.
[21] using the WINGX software package [22]. Non-hydrogen [10] N. Svenstrup, K.M. Rasmussen, T. Kruse, J. Becher, Synthesis (1994)
809.
atoms were refined with anisotropic thermal parameters,
[11] C. Wang, A.S. Batsanov, M.R. Bryce, J.A.K. Howard, Synthesis 11
whereas H-atoms were placed in idealized positions and (1998) 1615.
allowed to refine riding on the parent C atom. Molecular [12] G. Liu, G. Xue, W. Yu, W. Xu, Q. Fang, Acta Crystallogr., Sect. E 58
graphics were prepared using ORTEP3 [23]. A summary of (2002) o842t.
the crystal data, structure solution and refinement is given [13] E. Ribera, J. Veciana, E. Molins, I. Mata, K. Wurst, C. Rovira, Eur.
J. Org. Chem. (2000) 2867.
in Table 4.
[14] C. Rovira, J. Veciana, N. Santaló, J. Tarrés, J. Cirujeda, E. Molins, J.
Llorca, E. Espinosa, J. Org. Chem. 59 (1994) 3307.
Acknowledgements [15] D.L. Lichtenberger, R.L. Johnston, K. Hinkelmann, T. Suzuki, F.
Wudl, J. Am. Chem. Soc. 112 (1990) 3302.
This work was partially supported by FCT under con- [16] J. Llacay, I. Mata, E. Molins, J. Veciana, C. Rovira, Adv. Mater. 3
(1998) 330.
tracts POCTI/QUI/45108/2002, POCI/QUI/57528/2004
[17] (a) S. Bouguessa, A.K. Gouasmia, S. Golhen, L. Ouahab, J.M. Fabre,
and CICyT (CTQ2006-06333/BQU). This work was also Tetrahedron Lett. 44 (2003) 9275;
benefited from the ESF COST action D35 and the EC (b) S.-X. Liu, S. Dolder, E.B. Rusanov, H. Stoeckli-Evans, S.
Sixth Framework Programme MAGMANet NoE (Con- Decurtins, C.R. Acad. Sci. Paris, Chimie 6 (2003) 657;
tract No. 515767-2). (c) T. Devic, N. Avarvari, P. Batail, Chem. Eur. J. 10 (2004)
3697.
[18] G.M. Sheldrick, SADABS, Bruker AXS Inc., Madison, WI, USA, 2004.
Appendix A. Supplementary material [19] Bruker, SMART and SAINT, Bruker AXS Inc., Madison, WI, USA,
2004.
CCDC 626998 and 626999 contain the supplementary [20] A. Altomare, M.C. Burla, M. Camalli, G. Cascarano, G. Giacovazzo,
crystallographic data for 1 and 2 Æ CH2Cl2. These data A. Guagliardi, A.G.G. Moliterni, G. Polidori, R. Spagna, J. Appl.
Cryst. 32 (1999) 115.
can be obtained free of charge via http://www.ccdc.cam.
[21] G.M. Sheldrick, SHELXL97, Program for Crystal Structure Refine-
ac.uk/conts/retrieving.html, or from the Cambridge Crys- ment, University of Göttingen, Germany, 1997.
tallographic Data Centre, 12 Union Road, Cambridge [22] L.J. Ferrugia, J. Appl. Cryst. 32 (1999) 837.
CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: depos- [23] L.J. Ferrugia, J. Appl. Cryst. 30 (1997) 565.