Bis(calixcrown)tetrathiafulvalene receptors

Article abstract of DOI:10.1002/chem.200500878

A new class of electroactive receptors has been synthesized, built by covalent association of five subunits: two calixarene platforms for spatial organization, two polyether 3D cavities for cation binding, and one electroactive TTF unit to probe the compl

Full text of DOI:10.1002/chem.200500878

DOI: 10.1002/chem.200500878
Bis(calixcrown)tetrathiafulvalene Receptors
María-Jesffls Blesa, Bang-Tun Zhao, Magali Allain, Franck Le Derf, and Marc SallØ*[a]
Abstract: A new class of electroactive
receptors has been synthesized,built
by covalent association of five sub-
units: two calixarene platforms for spa-
tial organization,two polyether 3D
cavities for cation binding,and one
electroactive TTF unit to probe the
complexation event. Sodium complexa-
tion induces rigidification of the molec-
ular assembly,as shown by 1H NMR ti-
tration and single-crystal X-ray crystal-
lographic studies on free receptor 14
and a corresponding complex with two
bound sodium atoms per receptor (15-
(NaPF6)2). The calixarene units in
these receptors change from a pinched
cone conformation in the free ligand to
a symmetrical cone in the complex. Cy-
clovoltammetric studies validated the
electrochemical recognition concept of
these five-member assemblies.
Keywords: calixarenes
·
crown
compounds · cyclic voltammetry ·
host–guest systems · receptors
Introduction
the covalent association of the TTF moiety with a specific
binding unit. Although a broad variety of TTF derivatives
have been synthesized by different groups,only in a few
The tetrathiafulvalene (TTF) unit and its derivatives have
been at the forefront of different research topics for more
than thirty years. Besides the historical use as a precursor of
solid-state electroconducting organic metals[1] and recent
stimulating developments in exploring various other physical
properties,[1,2] this electroactive unit has recently emerged as
a very important redox brick in a great number of supra-
molecular systems,[3] such as catenanes,rotaxanes,pseudoro-
taxanes,and molecular shuttles,and also in dendrimer
chemistry.[4] These systems benefit from the well-defined
electrochemical properties of TTF derivatives,which are
known to be reversibly and easily oxidized to stable TTFC+
and TTF2+ states.
structures is the TTF unit associated with a rigid cavity,that
is,cyclodextrin,
[6]
calixarene,[7] or resorcinarene[8] platforms.
In the course of our project devoted to the preparation of
redox-responsive ligands,we recently illustrated the modu-
larity of the calixarene scaffold with the synthesis of calixar-
ene–TTF assemblies,linked either by aliphatic junctions as
the first models towards redox receptors,[9] or by amide
functions as molecular assemblies designed for anion recog-
nition.[10]
More approaches to supramolecular receptors involving
several cavities have been described during the past decade,
in particular by covalent association of two or more calixar-
ene units.[11] Besides their initial interest as synthetic targets
with exotic geometries,such multicavity architectures may
provide specific high-level host properties involving cooper-
ative effects,otherwise not reachable with monocavity deriv-
atives. On this basis,several types of linkers have been in-
troduced between two or more calix[4]arene units; they
range from simple aliphatic hydrocarbon chains to function-
alized linkers.[11,12] Moreover,a few examples of electroac-
We have been engaged for some years in the synthesis of
electroactive receptors incorporating the TTF unit,designed
to electrochemically sense or address the binding of a cat-
ionic guest.[5] These redox-responsive ligands are built from
[a] Dr. M.-J. Blesa,Dr. B.-T. Zhao,Dr. M. Allain,Dr. F. Le Derf,
Prof. M. SallØ
Laboratoire de Chimie et IngØnierie MolØculaire des MatØriaux
d’Angers (CIMMA)
Groupe Synth›se Organique et MatØriaux Fonctionnels
UMR CNRS 6200,UniversitØ d ’Angers
2 Bd Lavoisier,49045 Angers (France)
Fax : (+33)241-735-405
tive units have been grafted to or inserted into the calixar-
[13]
ene backbone,for example,ferrocene,
pyrrole,[14] thio-
phene,[15] p-quinone,[12a,16]
or
oligophenylenevinylene
motifs.[17] In some cases,such units may allow coupling of
recognition and conformational changes to redox perturba-
tion.[11]
E-mail: marc.salle@univ-angers.fr
Supporting information (1H NMR chemical shifts of 10–15 (Table 1)
1
and H NMR titration data with Na+ (Table 2)) for this article is
In the light of the structural properties of calixarenes,
crown ethers,and TTF,we launched the project for con-
available on the WWW under http://www.chemeurj.org/ or from the
author.
1906
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA,Weinheim
Chem. Eur. J. 2006, 12,1906 – 1914

FULL PAPER
structing a novel family based on the above three members.
Here we report on a family of double calix[4]arenes 10, 11
and their persubstituted analogues 12–15,which are tethered
by an electroactive TTF unit and have two three-dimension-
al (3D) cavities. To enhance the binding ability of intermedi-
ate receptors 10 and 11,we introduced two additional
metal-coordinating appendages per calixarene unit in 12–15
to give rise to 3D coordinating cavities. The calixarene scaf-
fold is used here as a 3D promoter. Such cryptand-like be-
haviour is somewhat similar to what is encountered with the
so-called bibracchial lariat ethers (BiBLE),in which the
three-dimensional character of the cavity is promoted by a
threefold substitution at the N junctions.[18]
(Scheme 1). A key step in our strategy is the [1+1] cyclo-
condensation between 4 or 5 and the p-tert-butylcalix[4]ar-
ene molecule. This reaction was carried out in refluxing ace-
tonitrile in the presence of cesium fluoride,used both as a
weak base and as a cyclization template. In this way,calix-
thiones 6 and 7 were obtained in reasonable yields of 58 and
18% respectively. No evidence of any higher cyclocondensa-
tion macrocycles,oligomers,or regioisomers (only dialkyla-
tion on the 1,3-rings of the calix[4]arene moiety took place)
was observed (Scheme 2).
A common procedure to build the TTF skeleton involves
dimerization–desulfurization of 1,3-dithiol-2-thiones in the
presence of trialkyl phosphite.[21] In our case,no coupling
product was observed on refluxing 6 or 7 with triethyl phos-
phite. This problem was solved by converting the thioxo re-
agents to their oxo analogues 8 and 9 with mercuric acetate
in chloroform/acetic acid (Scheme 2). Refluxing 8 and 9
with P(OEt)3 afforded TTF derivatives 10 and 11,disubsti-
tuted with calix[4]crown units,in 30 and 27% yield,respec-
tively.
The final step to the target three-dimensional receptors
12–15 involves tetraalkylation of the free phenolic rings. The
usual NaH/THF conditions and iodomethane[22] were em-
ployed to introduce four methyl groups into the lower rims
of the calixarene units in 10 and 11 to produce 12 and 13 in
70 and 60% yield,respectively (Scheme 3). Attempts to pre-
pare receptors 14 and 15 under the same conditions only af-
forded a mixture of mono-,di-,tri-,and tetraalkylated prod-
ucts when 2-bromoethyl methyl ether was employed. How-
ever,the use of phase-transfer conditions (toluene/50%
aqueous NaOH/tetrabutylammonium bromide)[23] resulted
in the target tetrasubstituted receptors 14 and 15 in 47 and
60% yield,respectively. Bis(calixcrown)tetrathiafulvalene
Herein we present 1) the synthesis of these novel five-unit
assemblies (i.e.,two calixarene platforms for spatial organi-
zation,two polyether 3D cavities for cation binding,and
one electroactive TTF unit to probe the complexation
1
event); 2) a H NMR conformational study of 12–15 on Na+
binding and the associated single-crystal X-ray structures of
both a free receptor and a bound form incorporating two
sodium cations; and 3) the electrochemical behaviour of
target receptors 12–15.
Results and Discussion
Synthesis: The synthetic route to target calix–crown–TTF as-
semblies 10–15 is outlined in Schemes 1–3. Thiones 2 and 3,
which incorporate two different poly(ethylene glycol)
chains,were prepared in good yields from the bis(tetraeth-
ylammonium)bis(1,3-dithiole-2-thione-4,5-dithiol)zincate
[(TEA)2[Zn(DMIT)2] (1)],[19] by adapting a classical proce-
dure,[20] and subsequently tosylated to produce 4 and 5
Scheme 1. Synthesis of the key 1,3-dithiol-2-thione intermediates.
Scheme 2. Synthesis of the calix–crown–TTF assemblies 10 and 11.
Chem. Eur. J. 2006, 12,1906 – 1914
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA,Weinheim
www.chemeurj.org
1907

M. SallØ et al.
tuted derivatives 12–15 and
their phenolic precursors 10
and 11. It is known that in 1,3-
bridged calix[4]arene deriva-
tives,the degree of cone distor-
tion can be correlated with the
Dd value observed between the
two types of ArH protons.[28]
On this basis,the calixarene
cone appears essentially sym-
metrical for 10 and 11 (Dd
ꢀ0.25 ppm),whereas the
Dd
values observed for 12–15 (Dd
ꢀ0.60 ppm) are indicative of
distorted cone conformations.
Such cone distortion from 10,
11 to 12–15 can be ascribed to
Scheme 3. Synthesis of the target calix–crown–TTF assemblies 12–15.
the steric requirement on O-al-
assemblies 10–15 were fully characterized by 1H and
13C NMR spectroscopy and mass spectrometry (MALDI
and/or ESI).
kylation,accompanied by the loss of H-bond stabilization
between phenolic OH groups and O atoms located on adja-
cent phenoxyl moieties. Additionally,the flattening of the
cone arising on alkylation is confirmed by the increase in
the Dd(ArCHaHbAr) value for 12–15 with respect to 10–
11.[29]
Slow evaporation of a solution of 14 in chloroform yield-
ed crystals suitable for X-ray structure determination.[30]
Host 14 has a crystallographic centre of symmetry at the
middle of the central C=C bond of the TTF moiety
(Figure 1). Each calixarene unit adopts a pinched cone con-
formation in the solid state,which confirms the distortion
anticipated on the basis of solution NMR data. Within the
same calixarene macrocycle,the phenyl rings intercept the
mean plane defined by the four carbon atoms of the methyl-
Structural analysis: NMR study and single-crystal X-ray
structures: Selected chemical shifts for calix–crown–TTF as-
semblies 10–15 are gathered in Table 1 (see Supporting In-
1
formation). Both H and 13C NMR spectra indicate that the
calixarene units in 10, 11 and 14, 15 only present in the cone
conformation.[11,22b,23,24] In particular,a pair of doublets as-
signed to diastereotopic bridging methylene protons (ArCHa-
HbAr) is present in each case. This conformation is attribut-
ed to stabilization of the cone through intramolecular hydro-
gen bonds (H-bonds) between phenolic rings in the case of
10 and 11,[11c,25] and to the bulkiness of the methoxyethyl
substituents,which prevents in-
terconversion between the dif-
ferent calixarene conformers
for 14 and 15.[26] Conversely,
the methylated derivatives 12
and 13 exist as a mixture of
conformers in slow exchange at
room temperature on the
500 MHz timescale,as was al-
ready observed for 1,3-dime-
thoxy calix[4]arene crowns.[24,27]
For 12 and 13,the methyl
group is not bulky enough to
prevent rotation around the
ArCH2Ar bridges. Therefore,
Table 1 in the Supporting Infor-
mation presents the chemical
shifts assigned to the major
conformers of 12 and 13,which
in each case correspond to the
cone form.
Noteworthily,significant
1H NMR spectral differences
exist between the fully substi- Figure 1. X-ray structure of calix–crown–TTF 14.
1908
www.chemeurj.org
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA,Weinheim
Chem. Eur. J. 2006, 12,1906 – 1914

Bis(calixcrown)tetrathiafulvalene Receptors
FULL PAPER
ene bridges (ArCH2Ar),with angles of about 68 8 (for phen-
oxyl groups linked to TTF) and about 908 (for phenoxyl
groups with pendant chains). In other words,two opposite
phenyl rings are perfectly parallel,whereas the other two
are significantly tilted. The polyether junctions located be-
tween the TTF part and both calixarene units generate,in
association with the four methoxyethyl pendant groups,two
3D cavities which are suitably organized to receive a guest
metal cation. The TTF unit ap-
tened and their interconversion is relatively slow on the
NMR timescale. In Table 2 in the Supporting Information,
this is in particular illustrated by the large Dd values for
both aromatic and tert-butyl protons. The addition of con-
trolled amounts of NaClO4 to solutions of 14 or 15 causes
the progressive appearance of a new set of signals for the
bound receptor and concomitant disappearance of the free-
ligand signals. An illustrative example is given in Figure 2,
pears essentially planar,a
requisite to retain its well-de-
fined reversible redox proper-
ties. Finally,the two calixarene
moieties are distributed on op-
posite sides of the TTF plane in
the five-member assembly 14
(calix–crown–TTF–crown–
calix).
1H NMR binding study: Ali-
quots of sodium perchlorate in
acetonitrile were added to a so-
lution of receptors 12–15 in
CDCl3/CD3CN (1/1).
Compounds 12 and 13: Com-
pounds 12 and 13 are confor-
mationally flexible in solution
at room temperature,and the
1H NMR spectra of the free li-
gands show mixtures of con-
Figure 2. 1H NMR spectra of 15 (CDCl3/CD3CN) in the presence of NaClO4: a) [Na+]/[15]=0.0; b) [Na+]/
[15]=0.5; c) [Na+]/[15]=1.0; d) [Na+]/[15]=2.0.
1
formers in solution,indicated in particular by the presence
of inequivalent aryl residues in each calixarene unit. The sig-
nals of 12 and 13 are relatively broad until the [Na+]/[li-
gand] ratio reaches unity. Stabilization of just one conforma-
tion is obtained after the addition of 2.00 equivalents of Na+.
Then the spectra simplify significantly and the signals
become sharper,which indicates that a tight and stable
sodium complex is formed and has the cone conformation.
The high symmetry of the cone in the complex is shown by
the equivalence of the signals of all aryl residues. No addi-
which shows the H NMR spectra of 15,without and with
NaClO4. Addition of sodium leads to a significant decrease
in these Dd values (to 0.01–0.02 ppm),which confirms the
formation of symmetrical cone cavities in the sodium com-
plexes. Moreover,sharpening of the signals is observed,
which points to formation of tight and stable complexes
with Na+.
Additionally,one can observe a significant low-field shift
(+0.31 ppm) of the singlet corresponding to the terminal
OCH3 group of the methoxyethyl appendages. This observa-
tion illustrates the complementary contribution of these
pendant groups to binding of the sodium cation,besides the
polyoxyethylene linkers located between the TTF and calix-
arene moieties.
1
tional changes are observed for the H NMR signals of the
sodium complexes of 12 or 13 on addition of more than
2.00 equivalents of Na+,which indicates a 1:2 stoichiometry
for these complexes. Table 2 in the Supporting Information
presents some selected 1H NMR chemical shifts of calix–
crown–TTF assemblies 12 and 13 (CDCl3/CH3CN) before
and after complexation with NaClO4. The high symmetry of
the calixarene cone cavity in the sodium complexes of 12
and 13 is clearly illustrated by the Dd values observed for
the aromatic and tert-butyl protons,which drop from about
0.39 (ArH) and 0.30 ppm (tBu) for the free ligands in cone
conformation to 0.01 ppm for each sodium complex.
Further binding studies were carried out with barium per-
chlorate. No evidence of complexation could be observed
1
from the H NMR data in this case,which illustrates the se-
lectivity of receptors 14 and 15 towards Na+ with respect to
Ba2+
.
Crystal structure of a disodium complex of a bis(calix-
crown)TTF: Single crystals for an X-ray diffraction study[31]
on a sodium complex of a bis(calixcrown)TTF assembly
were obtained by slow evaporation of a solution of 15 in
CH2Cl2/CH3CN in the presence of NaPF6 (CH3OH). As ex-
pected,two sodium atoms are bound per receptor (Figures 3
Compounds 14 and 15: The calixarene units of free recep-
tors 14 and 15 exclusively exist in the C2-symmetrical cone
conformation,in which the two distal aromatic units are flat-
Chem. Eur. J. 2006, 12,1906 – 1914
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA,Weinheim
www.chemeurj.org
1909

M. SallØ et al.
binding cavity,similar to what is observed with bibracchial
lariat ethers,for which the 3D character of metal binding is
promoted by the added contributions of a crown ether part
and two appended polyether arms.[18]
Electrochemical study: The electrochemical behaviour of
bis(calix-crown)TTF assemblies 12–15 was investigated by
cyclic voltammetry (CV) in dichloromethane/acetonitrile (1/
1). Derivatives of TTF are well known to undergo two suc-
cessive reversible one-electron redox processes. Compounds
12–15 behave similarly and exhibit the expected two succes-
sive redox processes in the usual range of potentials,that is,
very similar to those of the parent TTF(SMe)4 molecule.
Figure 5 shows a representative example for compound 13.
Figure 3. X-ray crystal structure of 15-(NaPF6)2(CH2Cl2) (solvent mole-
cule and anions omitted).
Figure 4. X-ray crystal structure of 15-(NaPF6)2(CH2Cl2) (solvent mole-
cule,anions,and tBu groups omitted).
and 4). The complex 15-(NaPF6)2 crystallizes in the space
Figure 5. Deconvoluted CV of 13 (0.26 mm) in CH3CN/CH2Cl2/TBAPF6
(0.10m) in the presence of increasing amounts of NaClO4; Pt electrode
(1 1.6 mm, v=100 mVsÀ1,versus Fc +/Fc).
¯
group P1 with one molecule of solvent (CH2Cl2). The cone
1
conformation observed in solution by H NMR spectroscopy
for both calixarene units of 15 is also observed in the solid
state. Contrary to free receptor 14,both calixarene moieties
are on the same side of the TTF plane in 15-(NaPF6)2,with
both cone axes at approximately 908 to the TTF plane. An-
other noticeable difference between the free receptor and
the sodium complex lies in the degree of symmetry of both
cones. In the complex,the four phenyl groups of each calix-
arene unit are tilted by 56–668 relative to the mean plane
defined by the four methylene carbon atoms. Therefore,
whereas the free ligand 14 shows a pinched cone conforma-
tion for both calixarene units (Figure 1),the disodium com-
plex of 15 exhibits essentially two symmetrical cones,as an-
ticipated from the H NMR data,for which complexation of
sodium ions results in simplification of the spectrum.
Each sodium cation of 15-(NaPF6)2 is hexacoordinated by
four phenolic oxygen atoms of the calixarene platform and
two O atoms of pendant methoxyethyl fragments. Neither
anion nor solvent molecule participates in metal coordina-
The first redox process corresponds to reversible oxidation
to a stable cation-radical state (E11=2 =0.04 V versus ferro-
cene). The second (E12=2 =0.34 V) is assigned to oxidation to
the dicationic state. As shown by 1H NMR studies,these
calix-crown-TTF-assemblies are able to bind two equivalents
of sodium cation per molecule. Therefore,we studied the
electrochemical response of these compounds on progres-
sive addition of a sodium perchlorate solution. No clear evi-
dence of electrochemical recognition of Na+ could be ob-
served for bis(calixcrown)TTF assemblies 12, 14,and 15.
However,the CV response of receptor 13 exhibits a slight
progressive positive shift of Epa1 (+30 mV) from zero to two
equivalents of added Na+ (Figure 5). No further variation of
potential is observed for higher concentrations of NaClO4,
in accordance with saturation of the system. Such electro-
chemical recognition process can be associated with both
conformational changes arising on Na+ complexation (as
1
À
tion. Five Na O distances per calixarene unit are in the
1
range of 2.33(3)–2.51(3) Š,while the sixth,which involves
one ethoxyethyl fragment,is slightly longer (2.70(4) Š).
Therefore,and in opposition to X-ray data obtained for an-
other calix[4]arene-based sodium complex incorporating
methoxyethyl pendant arms,[32] the appended methoxyethyl
groups of 15 clearly participate in sodium complexation,
giving rise to the expected 3D cavity in which the sodium
cation is isolated. To the best of our knowledge,this X-ray
structure is the first example of a disodium complex in the
calixcrown series; moreover,it establishes a cryptand-like
shown by the H NMR titration study) and to the electronic
effect of the bound cation on the electroactive TTF unit,as
is usually observed with redox-responsive ligands (the elec-
troactive TTF unit becomes more difficult to oxidize when a
positively charged guest is close).[5a,33] Interestingly,the
second redox process (E12=2) remains unchanged on addition
of Na+,that is,the metal complex no longer exists at this
potential. This is usually attributed to repulsive electrostatic
interactions between the ligand and the metal cation when
the TTF moiety is positively charged.[5a,33]
1910
www.chemeurj.org
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA,Weinheim
Chem. Eur. J. 2006, 12,1906 – 1914

Bis(calixcrown)tetrathiafulvalene Receptors
FULL PAPER
column to give 2 (CH2Cl2/AcOEt (1/2) then CH2Cl2/MeOH (20/1)) and 3
(CH2Cl2/MeOH (25/1)) as transparent red-orange oils. 2 (n=0): Yield
Conclusion
80%; 1H NMR (500 MHz,CDCl 3,298 K):
d=3.75–3.59 (m,12H;
In conclusion,we have developed a synthetic route to the
first electroactive calix–crown–TTF receptors. Their binding
ability for Na+ has been studied by 1H NMR titration,
which demonstrated pronounced conformational reorganiza-
tion on going from the free receptors to the sodium com-
plexes. Two cations are coordinated per TTF-based assem-
bly. The same observations were made in the solid-state,
since X-ray structures could be solved for a free receptor
and a disodium complex. Both metal cations are located in
3D pockets generated between the calixarene scaffold and
the TTF redox unit. The electrochemical behaviour (cyclic
voltammetry) of these five-membered assemblies (i.e.,two
calixarene platforms,two 3D polyether cavities,and one
electroactive TTF unit) is similar to that of classical TTF de-
OCH2),3.10 (t, J=5.9 Hz,4H; SCH 2),2.64 ppm (br,2H; OH); IR
(KBr): n˜ =1790 cmÀ1. 3 (n=1): Yield 78%; 1H NMR (500 MHz,CDCl
,
3
298 K): d=3.75–3.59 (m,20H; OCH 2),3.08 (t, J=6.3 Hz,4H; SCH 2),
2.64 ppm (br,2H; OH)
Tosylate derivatives 4 and 5: Triethylamine (2.5 g,25.5 mmol) dissolved
in CH2Cl2 (5 mL) was added dropwise over 30 min to a solution of 2 or 3
(4.0 mmol) and TsCl (2.50 g,13.1 mmol) in CH 2Cl2 (10 mL) at 08C. The
reaction mixture was stirred at room temperature under N2 for 24 h. The
organic phase was washed with water,dried over MgSO and evaporated
4
to yield an oily residue,which was purified by chromatography on a silica
column with petroleum ether/CH2Cl2 (gradient) to give 4 and 5 as red-
orange sticky oils. 4 (n=0): Yield 75%; 1H NMR (500 MHz,CDCl
,
3
298 K): d=7.79 (d, J=8.3 Hz,4H; ArH),7.34 (d, J=8.3 Hz,4H; ArH),
4.15 (t, J=4.8 Hz,4H; OCH 2),3.70–3.64 (m,8H; OCH 2),3.00 (t, J=
6.2 Hz,4H; SCH 2),2.46 ppm (s,6H; CH 3). (n=1): Yield 72%;
5
1H NMR (500 MHz,CDCl 3,298 K): d=7.79 (d, J=8.3 Hz,4H; ArH),
7.34 (d, J=8.3 Hz,4H; ArH),4.15 (t, J=4.8 Hz,4H; OCH 2),3.70–3.66
(m,8H; OCH 2),3.57 (t, J=4.8 Hz,8H; OCH 2),3.05 (t, J=6.3 Hz,4H;
SCH2),2.44 ppm (s,6H; CH 3).
+
rivatives,and an electrochemical response to Na complexa-
tion by a bis-calixcrown–TTF assembly could be detected.
Calix-1,3-dithiole-2-thiones 6 and 7: A suspension of p-tert-butylcalix[4]-
arene (1.520 g,2.3 mmol) and CsF (1.778 g,11.7 mmol) in dry CH 3CN
(100 mL) was refluxed for 1 h. Then a solution of 4 or 5 (2.3 mmol) in
dry CH3CN (100 mL) was slowly added over 8 h. The mixture was re-
fluxed for 24 h before the solvent was removed under reduced pressure.
The residue was dissolved in CHCl3 and brine was added. The organic
layer was separated and dried over MgSO4. The crude product obtained
after evaporation of the solvent was purified by flash chromatography
(gradient of CH2Cl2/AcOEt) to give 6 (from 4) and 7 (from 5) as orange
powders. 6 (n=0): Yield 58%; m.p. 97–1048C; 1H NMR (500 MHz,
CDCl3,298 K): d=7.22 (s,2H; OH),7.05 (s,4H; ArH),6.78 (s,4H;
ArH),4.32 (d, J=13.0 Hz,4H; ArCH 2Ar),4.12 (t, J=4.2 Hz,4H;
OCH2),4.04–3.99 (m,8H; OCH 2),3.31 (d, J=13.0 Hz,4H; ArCH 2Ar),
3.22 (t, J=6.2 Hz,4H; SCH 2),1.29 (s,18H; C(CH 3)3),0.95 ppm (s,18H;
C(CH3)3); 13C NMR (125.75 MHz,CDCl 3,298 K): d=211.3,150.5,149.7,
147.0,141.5,137.4,132.5,127.8,125.7,125.6,125.1,75.5,70.0,36.4,33.9,
Experimental Section
Instruments: 1H (500.13 MHz) and 13C NMR (125.75 MHz) spectra were
recorded on a Bruker AVANCE DRX 500 spectrometer. Chemical shifts
d are expressed in ppm relative to tetramethylsilane (TMS). Mass spectra
were recorded on a Bruker BIFLEX III (MALDI-TOF) spectrometer or
on a JEOL JMS 700 B/ES (ESI) spectrometer. Cyclic voltammetry (CV)
experiments were carried out on
a potentiostat–galvanostat EG&G
PARK 273 A,with solvents and electrolyte of electrochemical grade. CV
experiments were carried out at 298 K in a conventional three-electrode
cell equipped with a Pt disk working electrode (1 1 mm),a Pt wire
counterelectrode,and a reference electrode. All potentials are reported
versus the ferrocinium/ferrocene redox couple,and the electrochemical
response of ferrocene was recorded before and after each experiment.
33.8,31.7,31.5,31.4,31.3,31.0 ppm; FTIR (KBr):
n˜ =3447.8 (OH),
X-ray diffraction study: X-ray single-crystal diffraction data were collect-
ed at 293 K on a STOE-IPDS diffractometer for 14 and on a Bruker-
Nonius KappaCCD diffractometer for 15-(NaPF6)2(CH2Cl2)1,both equip-
1067.6 cmÀ1 (C=S); MS (MALDI-TOF): m/z: 987 [MC+]. 7 (n=1): Yield
18%; m.p. 90–918C; 1H NMR (500 MHz,CDCl 3,298 K): d=7.11 (s,2H;
OH),7.05 (s,4H; ArH),6.75 (s,4H; ArH),4.34 (d,
J=13.0 Hz,4H;
ped with
a graphite monochromator utilizing MoKa radiation (l=
ArCH2Ar),4.12 (t, J=4.2 Hz,4H; OCH 2),3.97 (t, J=4.2 Hz,4H;
OCH2),3.92 (t, J=4.2 Hz,4H; OCH 2),3.78–3.75 (m,8H; OCH 2),3.29
(d, J=13.0 Hz,4H; ArCH 2Ar),3.01 (t, J=5.9 Hz,4H; SCH 2),1.29 (s,
18H; C(CH3)3),0.92 ppm (s,18H; C(CH 3)3); 13C NMR (125.75 MHz,
CDCl3,298 K): d=211.4,150.6,149.7,146.9,141.4,136.9,132.5,127.8,
0.71073 Š). The structure were solved by direct methods and refined on
F2 by full-matrix least-squares techniques using the SHELX97 package.[34]
For 14,S and O atoms were refined anisotropically and C atoms isotropi-
cally,absorption was corrected by multiscan technique and the H atoms
were included in the calculation without refinement. For 15-(NaPF6)2-
125.5,125.0,75.8,71.1,71.0,70.2,69.9,36.3,33.9,33.8,31.7,31.4,31.0,
(CH2Cl2)1,S atoms were refined anisotropically and all others atoms iso-
À1
[35]
30.9 ppm; FTIR (KBr): n˜ =3448.7 (OH),1066.0 cm
m/z (%): 1075.35 [M++H] (100).
(C=S); ESI-MS:
tropically,absorption correction was carried out with SADABS
and
the H atoms were included in the calculation without refinement. For
both molecules,there are statistical disorders on most of the tert-butyl
groups,which were not treated because of missing data. CCDC-278002
and CCDC-278003 contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from the Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
Calix-1,3-dithiole-2-ones 8 and 9: A mixture of 6 (or 7) (0.3 mmol) in a
chloroform/acetic acid solution (20 mL/15 mL) and mercuric acetate
(0.640 g,2.0 mmol) was stirred under N at room temperature for 6 h.
2
The resulting white precipitate was filtered off on Celite and washed
thoroughly with CHCl3 (60 mL). The combined organic phases were
washed with NaHCO3 solution and water and then dried over MgSO4.
The solvent was removed in vacuo,and the crude product was purified
Materials: Unless otherwise noted,solvents and starting materials were
1
commercially available and used without further purification. H NMR ti-
on a silica gel column (CH2Cl2/AcOEt (5/1) to give 8 (from 6) or 9 (from
1
tration studies were carried out by adding small volumes of concentrated
solutions of the metal cation (as the perchlorate salt) in [D3]acetonitrile
to a solution of the calixarene receptor (1–3 mm) in CDCl3/CD3CN (1/1).
7) as a yellow powder. 8 (n=0): Yield 80%; H NMR (500 MHz,CDCl
298 K): d=7.31 (s,2H; OH),7.05 (s,4H; ArH),6.80 (s,4H; ArH),4.32
,
3
(d, J=13.0 Hz,4H; ArCH 2Ar),4.12 (t, J=4.7 Hz,4H; OCH 2),4.04 (t,
J=4.7 Hz,4H; OCH 2),4.00 (t, J=6.3 Hz,4H; OCH 2),3.31 (d, J=
13.0 Hz,4H; ArCH 2Ar),3.18 (t, J=6.3 Hz,4H; SCH 2),1.29 (s,18H; C-
1,3-Dithiol-2-thiones 2 and 3: 2-Chloroethoxyethanol or 2-[2-(2-chloroe-
thoxy)ethoxy]ethanol (5.9 mmol) and NaI (1.33 g,8.9 mmol) were dis-
solved in acetone (30 mL) and heated to reflux for 7 h. The mixture was
(CH3)3),0.96 ppm (s,18H; C(CH 3)3); 13C NMR (125.75 MHz,CDCl
,
3
298 K): d=189.7,150.5,149.6,147.0,141.4,132.6,128.2,127.7,125.6,
cooled to room temperature,whereupon (TEA) [Zn(DMIT)2] (1,0.860 g,
2
125.1,75.3,70.0,69.9,36.1,33.9,33.8,31.7,31.5,31.0 ppm; FTIR (KBr):
1.2 mmol) was added and the mixture was refluxed for 24 h. The mixture
was concentrated,and the residue dissolved in CH 2Cl2 (30 mL),washed
À1
n˜ =3410.9 (OH),1673.3 cm
(C=O); MS (MALDI-TOF): m/z: 970.06
with water (60 mL),dried with MgSO
and purified on a silica gel
[MC+]. 9 (n=1): Yield 100%; m.p. 1128C; 1H NMR (500 MHz,CDCl
,
4
3
Chem. Eur. J. 2006, 12,1906 – 1914
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA,Weinheim
www.chemeurj.org
1911

M. SallØ et al.
298 K): d=7.15 (s,2H; OH),7.05 (s,4H; ArH),6.75 (s,4H; ArH),4.34
(d, J=13.0 Hz,4H; ArCH 2Ar),4.12 (t, J=4.6 Hz,4H; OCH 2),3.98 (t,
J=4.6 Hz,4H; OCH ),3.92 (t, J=4.2 Hz,4H; OCH ),3.77–3.74 (m,8H;
OCH2),3.29 (d, J=13.0 Hz,4H; ArCH 2Ar),2.99 (t, J=4.1 Hz,4H;
SCH2),1.29 (s,18H; C(CH 3)3),0.93 ppm (s,18H; C(CH 3)3); 13C NMR
(125.75 MHz,CDCl 3,298 K): d=189.7,150.6,149.7,146.8,141.3,132.4,
1H NMR (500 MHz,CDCl 3/CD3CN 1/1+4 equivalents NaClO4,298 K):
d=7.26 (s,8H; ArH),7.25 (s,8H; ArH),4.26 (d,
J=12 Hz,8H;
ArCH2Ar),4.14 (t,8H; ArOCH 2),4.04 (t,16H; CH 2OCH2),3.80 (t,8H;
CH2OCH2) 3.93 (s,12H; OCH 3),3.74 (t,16H; CH 2OCH2),3.46 (d, J=
12 Hz,8H; ArCH 2Ar),3.06 (t,8H; SCH 2),1.19 (s,36H; C(CH 3)3),
1.18 ppm (s,36H; C(CH 3)3); FTIR on free 13 (KBr): n˜ =2960,2867,
1482,1120 cm À1; MS (MALDI-TOF): m/z: 2143.48 [MC+]; HR-ESI-MS:
m/z: 2163.9658 [MC++Na],calcd for C 122H164O16S8Na: 2163.9683.
2
2
128.0,127.6,125.4,125.0,75.7,71.1,70.9,70.1,69.8,53.3,36.1,33.8,31.8,
À1
31.7,31.4,30.9 ppm; FTIR (KBr): n˜ =3398.5 (OH),1670.3 cm
(C=O);
+
ESI-MS: m/z (%): 1081.7 [MC +Na] (100); HR-ESI-MS: m/z: 1081.4442
Tetrakis(methoxyethyl)bis(calix-crown)tetrathiafulvalenes 14 and 15: A
mixture of calixarene 10 or 11 (0.1 mmol),2-bromoethyl methyl ether
[M+C+Na],calcd for C 59H78O9S4Na: 1081.4426.
(0.198 mL,2.1 mmol) and Bu NBr (0.006 g) in a two-phase solution (tolu-
Bis(calix-crown)tetrathiafulvalenes 10 and 11: A suspension of 8 or 9
(0.30 mmol) in freshly distilled triethyl phosphite (5 mL) under N2 was
heated to reflux for 7 h. After cooling to room temperature,cold metha-
nol (50 mL) was added and the yellow precipitate which appeared was
washed with methanol and purified by a column chromatography on
silica gel to give pure 10 (CH2Cl2) (from 8) or 11 (CH2Cl2/AcOEt 10/1)
(from 9) as an orange powder. 10 (n=0): Yield 27%; m.p. 1708C;
1H NMR (500 MHz,CDCl 3,298 K): d=7.44 (s,2H; OH),7.05 (s,4H;
ArH),6.83 (s,4H; ArH),4.34 (d, J=13.0 Hz,4H; ArCH 2Ar),4.13–4.08
(m,8H; OCH ),3.96 (t, J=6.4 Hz,4H; OCH ),3.31 (d, J=13.0 Hz,4H;
4
ene (5 mL)/NaOH (50%,aq,1 mL)) was vigorously stirred at 100 8C for
6 h. After the mixture had been cooled,water (10 mL) was added and
the organic phase was separated and washed with 1n HCl and water.
The toluene solution was dried over MgSO4 then evaporated to dryness.
The solid residue was washed with MeOH and purified by column chro-
matography on silica gel to afford 14 (CH2Cl2/THF 60/1) or 15 (CH2Cl2,
CH2Cl2/AcOEt (10/1),toluene/acetone (10/1)) as an orange solid. 14 (n=
0): Yield 50%; m.p. 1628C; 1H NMR (500 MHz,CDCl 3,298 K): d=7.11
(s,8H; ArH),6.45 (s,8H; ArH),4.37 (d,
J=13 Hz,8H; ArCH Ar),4.20
2
2
2
(brt,16H; ArOCH 2),3.88–3.76 (m,24H; CH 2OCH2),3.47 (s,12H;
OCH3),3.11 (d, J=13 Hz,8H; ArCH 2Ar),3.05 (brt,8H; SCH 2),1.34 (s,
36H; C(CH3)3),0.81 ppm (s,36H; C(CH 3)3); 13C NMR (125.75 MHz,
CDCl3,298 K): d=154.3,151.8,154.2,144.3,135.6,131.9,127.8,125.4,
124.6,110.0,74.1,72.1,71.7,69.7,69.7,69.3,58.7,34.9,34.0,34.0,33.5,
ArCH2Ar),3.14 (t, J=6.4 Hz,4H; SCH 2),1.28 (s,18H; C(CH 3)3),
0.98 ppm (s,18H; C(CH 3)3); 13C NMR (125.75 MHz,CDCl 3,298 K): d=
150.6,149.6,146.9,141.3,132.6,128.6,127.8,125.5,125.0,110.2,75.3,
70.2,69.2,65.8,35.4,33.9,33.8,31.7,31.5,30.8 ppm; FTIR (KBr):
n˜ =
3413.2 cmÀ1 (OH); MS (MALDI-TOF): m/z: 1909 [MC+]; HR-ESI-MS:
m/z: 1931.7979 [MC++Na],calcd for C 110H140O12S8Na: 1931.8008. 11 (n=
1): Yield 27%; m.p. 1088C; 1H NMR (500 MHz,CDCl 3,298 K): d=7.26
31.7,31.5,30.7 ppm; FTIR (KBr): n˜ =1123 cmÀ1; MS (MALDI-TOF): m/
+
+
z: 2140.67 [MC ]; HR-ESI-MS: m/z: 2163.9690 [MC +Na],calculated for
122H164O16S8Na: 2164.9715. 15 (n=1): Yield 60%; m.p. 108–1128C;
C
(s,2H; OH),7.04 (s,4H; ArH),6.78 (s,4H; ArH),4.35 (d,
J=13.0 Hz,
1H NMR (500 MHz,CDCl 3,298 K): d=7.00 (s,8H; ArH),6.54 (s,8H;
ArH),4.44 (d, J=13 Hz,8H; ArCH 2Ar),4.18 (t, J=2.8 Hz,8H;
ArOCH2),4.13 (t, J=4.8 Hz,8H; ArOCH 2),3.60 (t, J=4.9 Hz,8H;
SCH2),3.80 (m,40H; CH 2OCH2),3.45 (s,12H; OCH 3),3.10 (d, J=
13 Hz,8H; ArCH 2Ar),1.25 (s,36H; C(CH 3)3),0.89 ppm (s,36H;
C(CH3)3); FTIR (KBr): n˜ =2961,1480,1123 cm À1; MS (MALDI-TOF):
4H; ArCH2Ar),4.12 (t, J=4.4 Hz,4H; OCH 2),3.99 (t, J=4.4 Hz,4H;
OCH2),3.92 (t, J=4.6 Hz,4H; OCH 2),3.76 (t, J=4.6 Hz,4H; OCH 2),
3.70 (t,J =6.2 Hz,4H; SCH 2),3.29 (d,J =13.0 Hz,4H; ArCH 2Ar),2.99
À1
(t, J=4.1 Hz,4H; SCH 2),1.29 (s,18H; C(CH 3)3),0.93 cm
(s,18H; C-
(CH3)3); 13C NMR (125.75 MHz,CDCl 3,298 K): d=150.5,149.7,146.8,
141.3,132.5,128.1,127.8,125.4,124.9,110.2,75.7,70.9,70.8,70.1,69.7,
+
+
35.5,33.8,33.7,31.6,31.4,30.9,30.8 cm
À1; FTIR (KBr): n˜ =3432.99 cmÀ1
m/z: 2318.60 [MC ],2341.52 [ MC +Na].
+
(OH); MS (MALDI-TOF): m/z: 2085.9 [MC +H]; HR-ESI-MS: m/z:
2084.9150 [MC+],calcd for C 118H156O16S8: 2084.9159.
Tetramethylated bis(calixcrown)tetrathiafulvalenes 12 and 13: Iodome-
Acknowledgement
thane (0.25 mL,4.00 mmol) was added to
a solution of 10 or 11
(0.04 mmol) and NaH (0.051 g,1.3 mmol) in dry THF (10 mL). The mix-
ture was stirred for 24 h at room temperature under N2. The reaction was
quenched with water (1 mL) and the solvents were removed under re-
duced pressure. The residue was dissolved in CH2Cl2 (20 mL) and
washed with water (30 mL),and the organic phase was separated and
dried over MgSO4. The residue was purified by chromatography on silica
gel (petroleum ether/THF 10/2) to give 12 (from 10) and 13 (from 11). 12
(n=0): Yield 70%; m.p. 1868C; 1H NMR (500 MHz,CDCl 3,298 K),
The “Conseil RØgional des Pays de la Loire” is gratefully acknowledged
for postdoctoral fellowships (B.T.Z. and M.J.B) as well as the “Programa
Europa XXI”CAI-DGA-CONSID+I (M.J.B.). M.J.B. thanks the CNRS
for a three-month position of associated researcher. The SCAS of the
University of Angers is thanked for spectroscopic characterization. M.S.
thanks the Institut Universitaire de France (IUF) for its financial sup-
port.
cone conformer: d=7.10 (s,ArH),6.46 (s,ArH),4.36 (d,
J=12.5 Hz,
ArCH2Ar),4.07 (s,OCH 3),3.13 (d, J=12.5 Hz,ArCH 2Ar),1.32 (s,C-
(CH3)3),0.82 (s,C(CH 3)3); other conformers are observed: d=7.18 (s,
[1] For recent reviews,see: a) Chem. Rev. 2004, 104,4887–5781 (the-
matic issue on Molecular Conductors); b) T. Otsubo ,K. Takimiya,
Bull. Chem. Soc. Jpn. 2004, 77,43–58; c) P. Fr›re,P. P. Skabara,
Chem. Soc. Rev. 2005, 34,69–98; d) J. L. Segura,N. Martín, Angew.
Chem. 2001, 113,1416–1455; Angew. Chem. Int. Ed. 2001, 40,1372–
1409; e) M. Brondstedt Nielsen,C. Lomholt,J. Becher, Chem. Soc.
Rev. 2000, 29,143–164.
ArH),7.00 (s,ArH),6.92 (s,ArH),6.69 (s,ArH),3.41 (s,OCH
3),3.10 (s,
OCH3),1.55 (s,C(CH 3)3),1.42 (s,C(CH 3)3),1.26 (s,C(CH 3)3),1.09 ppm
1
(s,C(CH )3). The H NMR spectrum is simplified on addition of 2 equiv-
3
alents of NaClO4 (12/NaClO4 complex,which only exists in a cone con-
formation): 1H NMR (500 MHz,CDCl 3/CD3CN 1/1+4 equivalents
NaClO4,298 K): d=7.26 (s,8H; ArH),7.25 (s,8H; ArH),4.19 (d,
12.5 Hz; 8H; ArCH2Ar),4.13 (t,8H; ArOCH 2),4.07 (t,16H;
J=
[2] Recent illustrations of various physical properties of TTF-based ma-
terials: a) M. Mas-Torrent,P. Hadley,S. T. Bromley,X. Ribas,J.
CH2OCH2),3.92 (s,12H; OCH 3),3.47 (d, J=12.5 Hz,8H; ArCH 2Ar),
3.28 (t,8H; SCH 2),1.18 (s,36H; C(CH 3)3,1.17 ppm (s,36H; C(CH 3)3);
FTIR on free 12 (KBr,cm À1): n˜ =2962,2867,1482,1121; MS (MALDI-
TOF): m/z: 1965.11 [MC+]; HR-ESI-MS: m/z: 1987.8717 [MC++Na],calcd
for C114H148O12S8Na: 1988.8666. 13 (n=1): Yield 60%; m.p. 105–1158C;
1H NMR (500 MHz,CDCl 3,298 K),cone conformer: d=7.11 (s,ArH),
6.44 (s,ArH),4.37 (d, J=12 Hz,ArCH 2Ar),4.00 (s,OCH 3),3.04 (d, J=
12 Hz,ArCH 2Ar),1.05 (s,C(CH 3)3),0.81 ppm (s,C(CH 3)3); other con-
formers are observed: d=7.22 (s,ArH),7.04 (s,ArH),6.90 (s,ArH),6.59
(s,ArH),3.29 (OCH 3) 2.95 (OCH3),1.43 (C(CH )3),1.33 ppm (C(CH )3).
Tarres,M. Mas,E. Molins,J. Veciana,C. Rovira,
2004, 126,8546–8553; b) P. Day,M. Kurmoo, J. Mater. Chem. 1997,
7,1291–1296; c) E. Coronado,C. J. Gómez-García, Chem. Rev.
J. Am. Chem. Soc.
1998, 98,273–296; d) L. Ouahab, Coord. Chem. Rev. 1998, 180,
1501–1531; e) C. Rovira, Chem. Eur. J. 2000, 6,1723–1729; f) J.
Garín,J. Orduna,R. andreu, Recent Res. Dev. Org. Chem. 2001, 5,
77–87; g) R. Andreu,M. J. Blesa,L. Carrasquer,J. Garin,J.
Orduna,B. Villacampa,R. Alcala,J. Casado,M. C. Ruiz Delgado,
J. T. Lopez Navarrete,M. Allain, J. Am. Chem. Soc. 2005, 127,
8835–8845; h) F. Dumur,N. Gautier,N. Gallego-Planas,Y. Sahin,
E. Levillain,N. Mercier,P. Hudhomme,M. Masino,A. Girlando,V.
3
3
The 1H NMR spectrum is simplified on addition of 2 equivalents of
NaClO4 (13/NaClO4 complex,which only exists in a cone conformation):
1912
www.chemeurj.org
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA,Weinheim
Chem. Eur. J. 2006, 12,1906 – 1914

Bis(calixcrown)tetrathiafulvalene Receptors
Lloveras,J. Vidal-Gancedo,J. Veciana,C. Rovira,
FULL PAPER
J. Org. Chem.
1 2002,354–359; j) M. Kumar,R. K. Mahajan,V. Sharma,H. Singh,
N. Sharma,I. Kaur, Tetrahedron Lett. 2001, 42,5315–5318; k) X.-S.
Zeng,L.-H. Weng,L.-X. Chen,H.-F. Ju,X.-B. Leng,X.-W. He,Z.-
Z. Zhang, Chin. J. Chem. 2001, 19,493–499.
2004, 69,2164–2177; i) J. Sly,P. Kasak,E. Gomar-Nadal,C. Rovira,
L. Gorriz,P. Thordarson,D. Amabilino,A. E. Rowan,R. J. Nolte,
Chem. Commun. 2005, 10,1255–1257.
[3] Selected examples: a) D. Amabilino,J. F. Stoddart, Chem. Rev. 1995,
95,2725–2828; b) J. O. Jeppessen,K. A. Nielsen,J. Perkins,S. A.
Vignon,A. Di Fabio,R. Ballardini,M. T. Gandolfi,M. Venturi,V.
Balzani,J. Becher,J. F. Stoddart, Chem. Eur. J. 2003, 9,2982–3007,
and references therein; c) S. S. Jang,Y. H. Jang,Y. H. Kim,W. A.
Goddard,A. H. Flood,B. W. Laursen,H. R. Tseng,J. F. Stoddart,
J. O. Jeppesen,J. W. Choi,D. W. Steuerman,E. DeIonno,J. R.
Heath, J. Am. Chem. Soc. 2005, 127,1563–1575; d) G. Doddi,G. Er-
colani,P. Mencarelli,A. Piermattei, J. Org. Chem. 2005, 70,3761–
[13] a) K. Moon,A. E. Kaifer, J. Am. Chem. Soc. 2004, 126,15016–
15017; b) A. J. Evans,S. E. Matthews,A. R. Cowley,P. D. Beer,
Dalton Trans. 2003, 24,4644–4650; c) B. Tomapatanaget,T. Tuntula-
ni,O. Chailapakul, Org. Lett. 2003, 5,1539–1542; d) P. D. Beer,E. J.
Hayes, Coord. Chem. Rev. 2003, 240,167–189; e) P. D. Beer,J.
Cadman, Coord. Chem. Rev. 2000, 205,131–155; f) P. A. Gale,Z.
Chen,M. G. B. Drew,J. A. Heath,P. D. Beer,
405–412.
Polyhedron 1998, 17,
[14] a) Z. Chen,P. A. Gale,P. D. Beer, J. Electroanal. Chem. 1995, 393,
113–117; b) P. D. Beer,S. Matthew,C. Zheng, 1998,US 5770453.
[15] a) M. J. Marsella,R. J. Newland,P. J. Carroll,T. M. Swager, J. Am.
3764; e) P. N. Cheng,P. T. Chiang,S. H. Chiu,
Chem. Commun.
2005,1285–1287; f) Y. Liu,A. H. Flood,P. A. Bonvallet,S. A.
Vignon,B. H. Northrop,H.-R. Tseng,J. O. Jeppesen,T. J. Huang,B.
Brough,M. Baller,S. Magonov,S. D. Solares,W. A. Goddard,C.-M.
Ho,J. F. Stoddart, J. Am. Chem. Soc. 2005, 127,9745–9759; g) Y.
Chem. Soc. 1995, 117,9842–9848; b) M. Giannetto,G. Mori,A.
Notti,S. Pappalardo,M. F. Parisi, Chem. Eur. J. 2001, 7,3354–3362;
c) A. Pailleret,D. W. M. Arrigan,J. K. Browne,M. A. McKervey,
Mater. Chem. 2002, 12,2665–2670.
J.
Liu,A. H. Flood,R. M. Moskowitz,J. F. Stoddart,
Chem. Eur. J.
2005, 11,369–385.
[16] a) M. Gómez-Kaifer,P. A. Reddy,C. D. Gutsche,L. Echegoyen,
Am. Chem. Soc. 1994, 116,3580–3587; b) T. D. Chung,D. Choi,
J.
[4] a) C. A Christensen,L. M. Goldenberg,M. R. Bryce,J. Becher,
Chem. Commun. 1998,509–510 and references therein; b) C. A.
Christensen,M. R. Bryce,J. Becher, Synthesis 2000, 12,1695–1704;
c) F. Le Derf,E. Levillain,G. TrippØ,A. Gorgues,M. SallØ,R. M.
Sebastian,A. M. Caminade,J. P. Majoral, Angew. Chem. 2001, 113,
230–233; Angew. Chem. Int. Ed. 2001, 40,224–227; d) A. Kanibo-
lotsky,S. Roquet,M. Cariou,P. Leriche,C. E. Turrin,R. De Bettig-
nies,A. M. Caminade,J. P. Majoral,V. Khodorkovsky,A. Gorgues,
Org. Lett. 2004, 6,2109–2112.
[5] a) J. Lyskawa,F. Le Derf,E. Levillain,M. Mazari,M. SallØ,L.
Dubois,P. Viel,C. Bureau,S. Palacin, J. Am. Chem. Soc. 2004, 126,
12194–12195; b) G. TrippØ,F. Le Derf,J. Lyskawa,M. Mazari,J.
Roncali,A. Gorgues,E. Levillain M. SallØ, Chem. Eur. J. 2004, 10,
6497–6509 and references therein; c) A. Gorgues,P. Hudhomme,
M. SallØ, Chem. Rev. 2004, 104,5151–5184.
S. K. Kang,S. K. Lee,S. K. Chang,H. Kim,
J. Electroanal. Chem.
1995, 396,431–439; c) D. Bethell,G. Dougherty,D. C. Cupertino, J.
Chem. Soc. Chem. Commun. 1995,675–676; d) M. Gómez-Kaifer,
P. A. Reddy,C. D. Gutsche,L. Echegoyen, J. Am. Chem. Soc. 1997,
119,5222–5229; e) K. C. Nam,S. O. Kang,H. S. Jeong,S. Jeon,
Tet-
rahedron Lett. 1999, 40,7343–7346; f) P. R. A. Webber,G. Z. Chen,
M. G. B. Drew,P. D. Beer, Angew. Chem. 2001, 113,2235–2238;
Angew. Chem. Int. Ed. 2001, 40,2265–2268; g) R. Vataj,H. Ridaoui,
A. Louati,V. Gabelica,S. Steyer,D. Matt,
J. Electroanal. Chem.
2002, 519,123–129; h) P. R. A. Webber,P. D. Beer,G. Z. Chen,V.
Felix,M. G. B. Drew, J. Am. Chem. Soc. 2003, 125,5774–5785; i) C.
-C. Zeng,J. Y. Becker, Tetrahedron 2004, 60,1643–1650.
[17] N. Armaroli,G. Accorsi,Y. Rio,P. Ceroni,V. Vicinelli,R. Welter,T.
Gu,M. Saddik,M. Holler,J.-F. Nierengarten,
New J. Chem. 2004,
[6] Y. Le Bras,M. SallØ,P. Leriche,C. Mingotaud,P. Richomme,J.
Møller, J. Mater. Chem. 1997, 7,2393–2396.
28,1627–1637.
[18] a) K. A. Arnold,L. Echegoyen,F. R. Fronczek,R. D. Gandour,D.
Richard,V. J. Gatto,B. D. White,G. W. Gokel, J. Am. Chem. Soc.
[7] J.-B. Regnouf-de-Vains,M. SallØ,R. Lamartine,
J. Chem. Soc.
Perkin Trans. 2 1997,2461–2462.
[8] S. Mendoza,L. A. Godínez,A. E. Kaifer, Supramol. Chem. 2004, 16,
1987, 109,3716–3721; b) G. W. Gokel,O. F. Schall in Comprehensive
Supramolecular Chemistry, Vol. 1 (Ed.: G. W. Gokel),Elsevier,
Oxford, 1996,pp. 97–152.
165–169.
[9] a) B.-T. Zhao,M.-J. Blesa,N. Mercier,F. Le Derf,M. SallØ,
J. Org.
[19] C. Wang,A. S. Batsanov,M. R. Bryce,J. A. K. Howard,
Synthesis
Chem. 2005,70,6254–6257; b) B.-T. Zhao,M.-J. Blesa,N. Mercier,F.
Le Derf,M. SallØ, Supramol. Chem. 2005, 17,465–468 .
1998,1615.
[20] M. B. Nielsen,Z.-T. Li,J. Becher, J. Mater. Chem. 1997, 7,1175–
1188.
[21] a) J. M. Fabre, Chem. Rev. 2004, 104,5133–5150 and references
therein.
[22] a) S. Shinkai,K. Fujimoto,T. Otsuka,H. L. Ammon, J. Org. Chem.
1992, 57,1516–1523; b) E. Ghidini,F. Ugozzoli,R. Ungaro,S. Har-
kema,A. Abu El-Fadl,D. N. Reinhoudt, J. Am. Chem. Soc. 1990,
112,6979–6985.
[10] B.-T. Zhao,M.-J. Blesa,N. Mercier,F. Le Derf,M. SallØ,
Chem. 2005, 29,1164–1167.
New. J.
[11] For books and selected reviews on calixarenes,see: a) C. D. Gutsche
in Calixarene, Vol. 1 (Ed.: J. F. Stoddard),The Royal Society of
Chemistry,Cambridge, 1989; b) J. Vicens,V. Bçhmer, Calixarene: A
Versatile Class of Macrocyclic Compounds,Kluwer Academic Pub-
lishers,Dordrecht, 1991; c) A. Ikeda,S. Shinkai, Chem. Rev. 1997,
97,1713–1734; d) C. D. Gutsche, Calixarene Revisited,The Royal
Society of Chemistry,Cambridge, 1998; e) L. Mandolini,R. Ungaro,
Calixarene in Action,Imperial College Press,London, 2000; f) Calix-
arenes 2001 (Eds.: Z. Asfari,V. Bçhmer,J. Harrowfield,J. Vicens),
Kluwer Academic Publishers,Dordrecht,The Netherlands, 2001.
[12] Recent examples: a) N. Kerdpaiboon,B. Tomapatanaget,O. Chaila-
pakul,T. Tuntulani, J. Org. Chem. 2005, 70,4797–4804; b) T. Nabe-
[23] I. Bitter,A. Grꢂn,B. ꢃgai,L. Tꢄke,
7840.
Tetrahedron 1995, 51,7835–
[24] A. P. Marchand,H.-S. Chong,T. P. Kumar,Z. Huang,S. Alihodzic,
W. H. Watson,K. Ejsmont, Tetrahedron 2002, 58,10205–10212.
[25] a) Y. Okada,M. Mizutani,F. Ishii,Y. Kasai,J. Nishimura,
Tetrahe-
dron 2001, 57,1219–1227; b) L. C. Groenen,E. Steinwender,
B. T. G. Lutz,J. H. van der Maas,D. N. Reinhoudt,
J. Chem. Soc.
shima,T. Saiki,K Sumihomo,S Akine,
Tetrahedron Lett. 2004, 45,
Perkin Trans. 1 1992, 2,1893–1898; c) P. D. J. Grootenhuis,P. A.
Kollman,L. C. Groenen,D. N. Reinhoudt,G. J. Van Hummel,F.
Ugozzoli,G. D. Andreetti, J. Am. Chem. Soc. 1990, 112,4165–4176.
[26] a) K. Iwamoto,K. Araki,S. Shinkai, J. Org. Chem. 1991, 56,4955–
4962; b) P. J. Dijkstra,J. A. Brunink,K. E. Bugge,D. N. Reinhoudt,
S. Harkema,R. Ungaro,F. Ugozzoli,E. Ghidini, J. Am. Chem. Soc.
1989, 111,7567–7575.
4719–4722; c) T. Nabeshima,T. Saiki,K Sumihomo,S Akine, Tetra-
hedron Lett. 2004, 45,6761–6763; d) T. Saiki,J. Iwabushi,S. Akine,
T. Nabeshima, Tetrahedron Lett. 2004, 45,7007–7010; e) A. Notti,S.
Occhipinti,S. Pappalardo,M. F. Parisi,I. Pisagatti,A. J. P. White,
D. J. Williams, J. Org. Chem. 2002, 67,7569–7572; f) G. T. Hwang,
B. H. Kim, Tetrahedron 2002, 58,9019–9028; g) V. Stastny,P.
Lhotꢁk,V. Michlovꢁ,I. Stibor,J. Sykora,
Tetrahedron 2002, 58,
[27] a) C. Fischer,S. Sarti,A. Castani,B. Carretoni,I. Manet,R. Schuur-
7207–7211; h) S. E. Matthews,P. Schmitt,V. Felix,M. G. B. Drew,
P. D. Beer, J. Am. Chem. Soc. 2002, 124,1341–1353; i) M. Makha,
P. J. Nichols,M. J. Hardie,C. L. Raston, J. Chem. Soc. Perkin Trans.
man,M. Guardigli,N. Sabbatini,R. Ungaro,
Chem. Eur. J. 2000, 6,
1026–1034; b) A. Casnati,A. Pochini,R. Ungaro,F. Ugozzoli,F.
Chem. Eur. J. 2006, 12,1906 – 1914
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA,Weinheim
www.chemeurj.org
1913

M. SallØ et al.
Arnaud,S. Fanni,M.-J. Schwing,R. J. M. Egberink,F. de Jong,D. N.
Reinhoudt, J. Am. Chem. Soc. 1995, 117,2767–2777.
40916 reflections collected,12959 unique ( Rint =0.17),restraints/pa-
rameters 3/761, R1=0.2376 and wR2=0.5268 for 5929 reflections
[28] a) I. Bitter ,ꢅ. Kꢆszegui,A. Grꢂn,P. Bakó,K. Pꢁl,A. Grofcsik,M.
with I>2s(I), R1=0.3565 and wR2=0.5845 for all data,GOF
À3
Kubinyi,B. Balꢁzs,G. Tóth,
Tetrahedron: Asymmetry 2003, 14,
1.821, À0.870<D1<1.918 eŠ
.
1025–1035; b) A. Arduini,S. Fanni,A. Pochini,A. R. Sicuri,R.
Ungaro, Tetrahedron 1995, 51,7951–7958.
[32] R. Abidi,L. Baklouti,J. M. Harrowfield,A. N. Sobolev,J. Vicens,
A. H. White, Org. Biomol. Chem. 2003, 1,3144–3146.
[29] a) I. Bitter,A. Grꢂn,G. Tóth,B. Balꢁzs,L. Tꢆke,
Tetrahedron 1997,
[33] a) F. Le Derf,M. Mazari,N. Mercier,E. Levillain,P. Richomme,J.
53,9799–9812; b) I. Bitter,A. Grꢂn,G. Tóth,B. Balꢁzs,G. Horvath,
L. Tꢆke, Tetrahedron 1998, 54,3857–3870.
[30] Crystal data for 14: C122H164O16S8, Mr =2143.02,orange plate,0.31ꢇ
Becher,J. Garin,J. Orduna,A. Gorgues,M. SallØ,
1999, 38,6096–6100; b) F. Le Derf,M. Mazani,N. Mercier,E. Levil-
lain,G. TrippØ,A. Riou,P. Richomme,J. Becher,J. Garin,J.
Inorg. Chem.
0.27ꢇ0.08 mm,monoclinic,space group
P21/n, a=14.006(2), b=
Orduna,N. Gallego-Planas,A. Gorgues,M. SallØ,
2001, 7,447–455; c) G. TrippØ,E. Levillain,F. Le Derf,A. Gorgues,
M. SallØ,J. O. Jeppensen,K. Nielsen,J. Becher,
2461–2464.
Chem. Eur. J.
31.987(4), c=16.785(2) Š, b=103.75(1)8, V=7304(2) Š3, Z=2,
1calcd =0.974 gcmÀ3
,
m(MoKa)=0.172 mmÀ1
,
F(000)=2304, qmin
=
=
Org. Lett. 2002, 4,
1.788, qmax =24.038,41533 reflections collected,10764 unique ( Rint
0.34),restraints/parameters 1/313, R1=0.1331 and wR2=0.3092 for
1538 reflections with I>2s(I), R1=0.3973 and wR2=0.4321 for all
[34] G. M. Sheldrick,SHELX97 (includes SHELXS97,SHELXL97,
CIFTAB,and SHELXA),Programs for crystal structure analysis
(Release 97-2),University of Gçttingen,Germany, 1998.
[35] G. M.Sheldrick,SADABS,Version 2.10,Bruker Nonius area detec-
tor absorption correction,Madison,Wisconsin,USA, 2003.
À3
data,GOF 0.726, À0.355<D1<0.786 eŠ
.
[31] Crystal data for 15-(NaPF6)2(CH2Cl2)1: C131H182Cl2F12Na2O20P2S8,
Mr =2740.07,yellow plate,0.23ꢇ0.22ꢇ0.015 mm,triclinic,space
¯
group P1, a=12.580(3), b=23.707(4), c=26.164(6) Š, a=84.93(2),
b=80.85(2), g=86.36(2)8, V=7664(3) Š3, Z=2, 1calcd =1.187 gcmÀ3
m(MoKa)=0.249 mmÀ1
F(000)=2900, qmin =2.108, qmax =20.008,
,
Received: July 25,2005
Published online: January 18,2006
,
1914
www.chemeurj.org
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA,Weinheim
Chem. Eur. J. 2006, 12,1906 – 1914