Columnar mesophases controlled by counterions in potassium complexes of dibenzo[18]crown-6 derivatives

Article abstract of DOI:10.1002/chem.200901173

Dibenzo[18]crown-6 derivatives 1 with two lateral tetraalkyloxy oterphenyl units were prepared and converted to the corresponding complexes KX·1 (X = halide, BF₄, PF₆, SCN) and NH₄PF ₆·1. Complexation was probed

Full text of DOI:10.1002/chem.200901173

DOI: 10.1002/chem.200901173
Columnar Mesophases Controlled by Counterions in Potassium Complexes
of Dibenzo[18]crown-6 Derivatives
Martin Kaller,[a] Stefan Tussetschlꢀger,[a] Peter Fischer,[a] Christopher Deck,[a]
Angelika Baro,[a] Frank Giesselmann,[b] and Sabine Laschat*[a]
Abstract: Dibenzo[18]crown-6 deriva-
tives 1 with two lateral tetraalkyloxy o-
terphenyl units were prepared and con-
verted to the corresponding complexes
KX·1 (X=halide, BF4, PF6, SCN) and
NH4PF6·1. Complexation was probed
by MALDI-TOF spectrometry and
NMR spectroscopy. Downfield shifts of
1H NMR signals for complexes with
soft anions Br, I, SCN, and PF6 indicat-
ed the presence of tight ion pairs,
whereas complexes with hard anions F,
Cl, or BF4 showed no or little shifts. In
13C NMR spectra, upfield shifts were
detected for soft anions. The character
of the anion also influenced the meso-
morphic properties of complexes MX·1
(M=K, NH4), which were investigated
by differential scanning calorimetry
(DSC), polarizing optical microscopy
(POM), and XRD in comparison to
neat 1. Hard anions slightly stabilize or
even destabilize the mesophase. Soft
anions, however, improve the meso-
morphic properties yielding mesophas-
es with up to 708C phase widths in the
case of KI·1, KPF6·1, and NH4PF6·1.
For complexes KSCN·1 with a soft and
bridging anion, the balance between
mesophase stabilization and high order
is shifted in favor of the plastic crystal
phase.
Keywords: anions
· crown com-
pounds · ion pairs · liquid crystals ·
mesophases
Introduction
of salts to mesogenic crown ethers and azacrowns may
induce or stabilize mesophases.[5–7] The combination of
crown ethers bearing mesogenic groups is of particular inter-
est, because the properties of these hybrid systems lead to a
variety of useful applications such as membranes containing
ion-selective transport channels,[8] amphiphilic metallomeso-
gens with high charge-carrier mobilities for high-perfor-
mance organic field effect transistors,[9] conducting wires,[10]
helical fibers that self-assemble at gel–graphite interfaces,[11]
and organic gelators.[10b,e,12] Previously, we reported on
[15]crown-5 derivatives with ether-substituted lateral ortho-
terphenyl units showing upon NaI complexation a change of
the mesophase type from SmA phases spanning 308C to col-
umnar mesophases with a broad temperature range up to
1408C.[13] In contrast, neither the uncomplexed nor the NaI-
complexed [15]crown-5 derivatives bearing gallic ester-sub-
stituted lateral ortho-terphenyl units displayed any meso-
morphism.[14] However, when the gallic ester units were re-
placed by alkanoic acid esters, the addition of NaI induced
columnar mesophases.[14] For [18]crown-6 derivatives with
two ether-substituted lateral ortho-terphenyl units, a com-
pletely different picture emerged.[15] Even uncomplexed de-
rivatives with short chain lengths of five C atoms displayed
columnar mesophases, albeit with relatively small phase
widths. Upon addition of KI, the phase stabilities were sig-
The development of materials that allow for significant
modification of their structural and physical properties by
specific chemical or physical stimuli have received increas-
ing interest among material chemists.[1] Additives are widely
regarded to change the mesomorphic properties of thermo-
tropic liquid-crystalline compounds to a remarkable extent.
Prominent examples are additives that induce the formation
of liquid-crystalline charge-transfer complexes,[2] and chiral
dopants that induce a cholesteric phase in an achiral nemat-
ic[3] or ferroelectricity in a smectic host phase.[4] In 1993,
Percec, Ungar, and co-workers discovered that the addition
[a] Dipl.-Chem. M. Kaller, Dr. S. Tussetschlꢀger,
Priv.-Doz. Dr. P. Fischer, Dipl.-Chem. C. Deck, Dr. A. Baro,
Prof. Dr. S. Laschat
Institut fꢁr Organische Chemie der Universitꢀt Stuttgart
Pfaffenwaldring 55, 70569 Stuttgart (Germany)
Fax : (+49)711-685-64285
E-mail: sabine.laschat@oc.uni-stuttgart.de
[b] Prof. Dr. F. Giesselmann
Institut fꢁr Physikalische Chemie der Universitꢀt Stuttgart
Pfaffenwaldring 55, 70569 Stuttgart (Germany)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200901173.
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FULL PAPER
nificantly increased, with phase widths up to 708C. Previous-
ly, Mochizuki and Wakisaka[16] and Olsher[17] published the
importance of counterions on the physical properties of non-
mesogenic crown ether salt complexes, and Tschierske et al.
observed for calamitic mesogens with lateral crown ethers
increased clearing points and phase widths of the lyotropic
columnar mesophases upon addition of KI as compared
with KBr or KCl.[5e] Thus we anticipated that counterions
might also play a major role regarding phase sequence and
stability of liquid-crystalline crown ethers. To gain a more
detailed understanding of such structure–property relation-
ships, we synthesized a series of crown ether complexes
MX·1a–g with different counterions (Scheme 1) and investi-
gated the mesomorphic properties in comparison with the
uncomplexed crown ethers 1a–g. The results are discussed
below.
(Scheme 1). After filtration and evaporation of the solvent,
the corresponding complexes MX·1a–g were isolated quan-
titatively. The 1:1 complexation was verified by elemental
analysis for MX·1g (MX=KI, KSCN, KPF6, NH4PF6) and
we thus concluded 1:1 complexes with 1a–f as well. The ele-
mental analysis of KF·1g revealed the presence of one
MeOH molecule in the unit cell. In the case of complexes
KX·1g in which X=Clꢀ, Brꢀ, or BF4 , the 1:1 stoichiometry
ꢀ
was based on spectroscopic results (MALDI-TOF MS,
NMR spectroscopy) because proper elemental analyses
could not be obtained. It must be noted that the formation
of 1:1 complexes agrees well with earlier results by the
groups of d’Amboise and Sato on KCl and KBr complexes
of unfunctionalized [18]crown-6 and dibenzo[18]crown-6.[21]
MALDI-TOF spectra of crown ether complexes: The
MALDI-TOF spectrum of free crown 1g revealed an inten-
sive molecular ion peak at m/z 2137.7 and two smaller peaks
at m/z 2160.5 and 2176.7 for the [M+Na]+ and [M+K]+ ad-
ducts, respectively (Figure 1a). The presence of [M+Na]+
can be attributed to traces of sodium salts in the potassium-
Scheme 1. Prepared [18]crown-6 derivatives 1 and their complexes.
Results and Discussion
Syntheses: The known crown ethers 1a–e were prepared as
published.[15] For derivatives 1 f and 1g with chain lengths of
C11 and C12, respectively, the literature procedure was modi-
fied starting with a Dakin oxidation[18] of commercially
available 5-bromo-2-hydroxybenzaldehyde to provide 4-bro-
mocatechol, Williamson etherification, and formation of the
respective 4,4,5,5-tetramethyl-1,3,2-dioxaborolane. Subse-
quent Suzuki coupling with tetrabromodibenzo[18]crown-
6[19] gave 1 f and 1g in 82 and 83% yield, respectively (see
the Supporting Information). The purity of 1a–g was veri-
fied by elemental analysis. By following a modified protocol
by Pedersen et al.,[20] crown ethers 1 (1 equiv) were added
to a solution of the respective potassium or ammonium salts
(1.5 equiv) in MeOH and heated for 18 h at 408C
Figure 1. MALDI-TOF spectra. a) Uncomplexed crown ether 1g and
b) complex KI·1g.
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S. Laschat et al.
free matrix and [M+K]+ is due to potassium impurities in
sodium. In contrast, the MALDI-TOF spectrum of complex
KI·1g shows the [M+K]+ at m/z 2176.7 as the most inten-
sive peak (Figure 1b). The signals for [M]+ and [M+Na]+
are caused by potassium–sodium exchange with the matrix
and loss of potassium under the experimental conditions.
The spectra shown are typical for all complexes KX·1.
who observed downfield shifts when only a 1:1 salt/crown
complex was present. Taking these results into account, we
conclude from the H NMR spectroscopic data that 1:1 com-
1
plexes were formed upon salt addition to 1 f. The downfield
shift increased with increasing softness of the anion, most
obvious for KF<KCl<KBr<KI, whereby KBF4 with hard
anion resembles KF. The spectra of KX·1 f with X=SCNꢀ
For the complexes NH4PF6·1, [M]+ was observed as the
most intense peak (see the Supporting Information). Addi-
tionally, the peaks for [M+Na]+ and [M+K]+ were detect-
ed, but both being low in intensity so that their appearance
can be attributed to impurities in the matrix. Unfortunately,
[M+NH4]+ could not be observed, thereby indicating that
the latter compounds are not stable under MALDI condi-
tions and lose the cation under the applied high vacuum.
and PF6 , which are capable of interaction with K+ through
ꢀ
more than one atom, slightly differ from those of halides.
As suggested by Lockhart etal.,[23] the considerable down-
field shifts of H-b in complexes with KBr, KI, KSCN, and
KPF6 may be caused by the presence of tight ion pairs,
while the different solvent interactions with the bridging
NMR spectra of crown ether complexes: The complexation
of crown ethers 1 can also be monitored by 1H and
13C NMR spectroscopy (Figures 2 and 3). As shown in
Figure 2 for the series free crown 1 f and complexes MX·1 f,
the signals of the crown protons H-a and H-b (see
1
Scheme 1) undergo a downfield shift in the H NMR spec-
trum upon complexation.
This effect is most pronounced for the signals of H-b,
which were clearly shifted downfield from d=4.00 ppm for
neat 1 f to d=4.17 ppm upon addition of KBr and even
overlapped with the H-a signals at dꢁ4.29 ppm for complex
KI·1 f. A smaller shift to d=4.15 ppm was found for com-
plex KSCN·1 f. In contrast, a maximum shift of the H-a sig-
nals was observed from d=4.24 ppm (free 1 f) to d=
4.31 ppm for KSCN·1 f. In the series of halides, the down-
field shift of H-a increased with the size of the anion in the
order Fꢀ ꢁClꢀ <Brꢀ <Iꢀ. Although the spectrum of complex
KBF4·1 f showed similar features to those observed for
KF·1 f, a clear shift of both H-a and H-b was recorded for
complex KPF6·1 f.
Figure 2. 1H NMR spectra (300 MHz, CD2Cl2) of crown ether 1 f and its
complexes KX·1 f as well as NH4PF6·1 f.
Similar effects were found
earlier by Chan and Live in a
detailed study of spectral
changes in various diben-
zo[18]crown-6
complexes.[22]
The downfield shift of the ether
protons was explained to arise
from 1) a small increase in the
dihedral
angle
of
the
OCH2CH2O fragment upon ion
complexation, 2) an electric
field caused by the presence of
the salt, and 3) a different align-
ment of the solvent molecules
around the complex. Further-
more, the salt-induced shift is a
linear function of the cation-to-
crown concentration (up to a
1:1 ratio), thus indicating a 1:1
stoichiometry. This finding was
Figure 3. 13C NMR spectra (75 MHz, CD2Cl2) of crown ether 1 f and its complexes KX·1 f as well as
confirmed by Lockhart et al.,[23] NH4PF6·1 f.
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Dibenzo[18]crown-6 Derivatives
FULL PAPER
ꢀ
SCNꢀ and PF6 anions[22] could be responsible for the small-
plexes MX·1a–g were studied by differential scanning calo-
rimetry (DSC), polarizing optical microscopy (POM), and
X-ray scattering (WAXS, SAXS). The detailed results are
summarized in Tables S1–S10 in the Supporting Informa-
tion.
er downfield shifts of H-b (Figure 2). In complexes with KF,
KCl, and KBF4, ion pairing seems to be unimportant, and
thus these anions can be considered ꢃnakedꢄ anions in analo-
gy to results found for the system KCl·[18]crown-6.[24]
13C NMR spectroscopy is generally less sensitive to
changes in the solvent environment[22] and conformational
changes and ion pairing dominate the chemical shifts in the
spectra. Thus, upfield shifts observed for the complex
KSCN·dibenzo[18]crown-6 could be clearly attributed to the
presence of tight ion pairs by investigating the spin-lattice
relaxation times.[25]
Crown ether complexes have also been described by sev-
eral authors to have identical structures in solution and in
the solid state,[22,23,25] and the presence of ion pairs could be
verified by X-ray studies on the complexes of dibenzo[18]-
crown-6 with KSCN, KPF6, and NH4PF6, respectively, in
which the anion is located close to the crowned potassium.
In the case of KSCN, the ion pairs are linked by the bridging
thiocyanate.[26] Hexafluorophosphate turned out to be a
bridging anion as well, since each crowned K+ coordinates
two fluorine atoms, and two of the remaining fluorine atoms
coordinate the neighboring crowned K+.[27] For KBr·diben-
zo[18]crown-6, ion pairing is less important or even absent
because several solvent molecules are vital for the structure
and the stability of the complex.[28]
As previously reported,[15] for free crown ethers 1a–e with
chain lengths of C6 to C10, enantiotropic mesophases were
observed between 68 and 968C. However, compounds 1 f
and 1g with undecyl and dodecyl side chains displayed mono-
tropic mesophases. Derivative 1g displayed a phase transi-
tion of the isotropic liquid in the mesophase at 808C and a
crystal-to-crystal transition at 718C upon first cooling. Upon
second heating, 1g showed a crystal-to-crystal transition at
268C and cleared at 798C into an isotropic liquid. Upon
cooling from the isotropic liquid, crown ether 1 f showed a
transition to the liquid-crystalline phase at 808C, a transition
from the mesophase to the crystalline phase at 738C and
two crystal-to-crystal transitions at 38 and 298C (Figure 4a).
Upon addition of salts to crown ether derivatives 1, we
also observed in the 13C NMR spectra anion-dependent up-
field shifts for C-1, C-2, C-3, C-6, and C-a, C-b (for number-
ing, see Scheme 1), as exemplified by 1 f and complexes
MX·1 f in Figure 3. The most significant upfield shift was de-
tected for the aryl C atom C-3/C-6 in the complexes with
KBr, KI, KSCN, and KPF6. The maximum shift of Dd
ꢁ2 ppm (from free crown 1 f to the KPF6 complex) corre-
sponds with literature data of related systems[25] and reveals
similar trends of the counterions as discussed above for
1H NMR spectra.
Regarding the NH4PF6·1 f complex (see Figures 2 and 3),
1
the following results were obtained. In the H NMR spec-
trum, a downfield shift of H-a as large as that for the KSCN
complex was found, while the shift for the H-b signals is ap-
proximately in the region of the corresponding KPF6 com-
plex. The upfield shift of C-3/C-6 in the 13C NMR spectrum
is smaller than the KPF6 complex, and the other relevant C
atoms show a similar tendency. This finding indicates that
the spectral properties are dominated by the anion rather
than the cation.
Figure 4. DSC curves of a) free derivative 1 f and b) complex KF·1 f
(heating/cooling rate 5 Kminꢀ1). Cr=crystal, Colr =rectangular colum-
nar, Colh =hexagonal columnar, I=isotropic liquid.
Upon second heating, a crystal-to-crystal transition at 288C
and isotropic melting at 838C were observed.
As the example of 1 f shows (Figure 5a), either focal-conic
or spherulithic textures typical for columnar mesophases
were detected by polarizing optical microscopy. The line de-
fects in the left part of the texture indicate ordered colum-
nar phases.
The DSC data of the potassium halide complexes of
crown ethers 1 upon first cooling are illustrated in Fig-
ure 6a–d.
In consideration of the literature findings[22–28] and our
NMR spectroscopic data, we assume that the anions of the
complexes MX·1 with KF, KCl, and KBF4 are not located at
fixed positions (small shifts), whereas ion pairs are present
in complexes with KBr, KI, KSCN, KPF6, and NH4PF6
(large shift). These ion pairs are presumably less tight in
KBr complexes relative to the other salts.
Although the KF complexes of 1a and 1b with hexyl and
heptyl chains were nonmesogenic, KF complexes of deriva-
tives 1c–g with C8 to C12 side chains formed mesophases be-
Mesomorphic properties of crown ether complexes: Meso-
morphic properties of crown ethers 1a–g and their com-
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S. Laschat et al.
Figure 5. Textures of crown ether 1 f and potassium halide complexes
KX·1 as seen between crossed polarizers upon cooling from the isotropic
phase. a) Neat 1 f at 798C (cooling rate 5 Kminꢀ1, magnification ꢅ200);
b) complex KF·1e at 708C (cooling rate 2 Kminꢀ1, magnification ꢅ100);
c) complex KCl·1g at 688C (cooling rate 10 Kminꢀ1
, magnification
ꢅ200); d) complex KBr·1 f at 778C (cooling rate 10 Kminꢀ1, magnifica-
tion ꢅ200); e) initial texture formation of complex KI·1 f at 1208C; and
f) the same texture after 10 min (cooling rate 0.1 Kminꢀ1, magnification
ꢅ200).
tween 63 and 798C, albeit with small mesophase widths of
2–148C (Figure 6a). For complexes KF·1c–f with chain
lengths between C8 and C11 monotropic behavior (Fig-
ure 4b), and for KF·1g with dodecyl side chains enantiotrop-
ic behavior was observed. Upon cooling, compounds KF·1c–
f gave focal-conic textures by POM, as shown in Figure 5b
for derivative 1e.
Figure 6. Mesophase stabilities of the potassium halide complexes
a) KF·1, b) KCl·1, c) KBr·1, and d) KI·1 upon first cooling (first heating
The KCl complexes of 1 produced some puzzling results.
Upon cooling, the KCl complexes of 1a–e crystallized di-
rectly from the isotropic liquid (Figure 6b). In the case of
KCl·1d, an additional crystal-to-crystal transition was ob-
served. However, in contrast to these DSC data, a focal-
conic fan-shaped texture was detected for KCl·1e under the
microscope. Complex KCl·1 f with C11 chain displayed an
isotropic-to-mesophase transition at 808C, a crystallization
at 768C, and two crystal-to-crystal transitions at 36 and
298C upon first cooling. Upon second heating, only crystal-
to-crystal transitions (27 and 418C) together with isotropic
melting at 818C were detected. In contrast, complex KCl·1g
showed a crystal-to-crystal transition at 698C, a crystal-to-
mesophase transition at 838C, and a clearing point at 898C
upon first heating (see Table S3 in the Supporting Informa-
tion). Upon cooling from the isotropic liquid, however,
KCl·1g crystallized directly. Thus, both complexes showed
&
&
in the case of KCl·1g with C12 side chain). Key: =crystal, =Col.
monotropic behavior. Upon rapid cooling (10 Kminꢀ1) of
KCl·1g, a fan-shaped texture was detected by POM (Fig-
ure 5c).
In the series of complexes KBr·1a–g, a minimal chain
length of C10 (1e) was required to observe mesomorphism
(Figure 6c). In all cases, monotropic behavior was found
with small mesophase widths of 8–128C. Figure 5d shows
fan-shaped textures of KBr·1 f, which are typical for the
mesogenic KBr-complexed crowns 1.
As described earlier[15] and in contrast to the other potas-
sium halides, KI had a remarkable stabilizing effect on the
columnar mesophases of crown ethers 1. The whole series
KI·1a–g displayed enantiotropic mesophases between 76
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Dibenzo[18]crown-6 Derivatives
FULL PAPER
and 1498C, thus mesophase widths up to 738C were ach-
ieved (Figure 6d). Upon slow cooling (0.1 Kminꢀ1) of KI·1 f
from the isotropic liquid, star-shaped domains appeared
under the POM (Figure 5e), which transformed into fan-
shaped textures upon further cooling (Figure 5f).
Figure 7a–c summarizes the DSC data of the complexes
ꢀ
ꢀ
KX·1 with the counterions X=BF4 , PF6 , and SCNꢀ. As
can be seen from Figure 7a, tetrafluoroborate complexes
Figure 8. Textures of potassium complexes KX·1 as seen between crossed
polarizers upon cooling from the isotropic phase. a) Complex KBF4·1g at
808C (cooling rate 10 Kminꢀ1, magnification ꢅ100); b) complex KPF6·1d
at 1138C (cooling rate 10 Kminꢀ1, magnification ꢅ200); c) initial texture
formation of complex KSCN·1e at 1728C; and d) the same texture after
10 min (cooling rate 10 Kminꢀ1, magnification ꢅ200).
significant stabilization of the mesophases. Enantiotropic
mesomorphism between 72 and 1508C was observed for
complexed derivatives 1a,b,d–f. In the case of 1c, however,
the transition in the mesophase upon first cooling was not
visible by DSC and POM, but upon heating a crystal-to-
mesophase transition at 848C was detected. Complex
KPF6·1d gave a star-shaped texture under POM conditions
upon cooling (Figure 8b), which is characteristic for this
series of complexed crown ethers.
The DSC data obtained for complexes KSCN·1a–g are
shown in Figure 7c. The complexes of 1a–f displayed enan-
tiotropic (meso)phases in the range of 72–1808C. In con-
trast, KSCN·1g crystallized directly upon first cooling, and
upon second heating only isotropic melting was observed.
Although the textures obtained by POM, for example, for
KSCN·1e (Figure 8c and d), looked somewhat similar to the
textures of KI·1e, an assignment was only possible by X-ray
diffraction, resulting in a plastic crystalline phase (see
below). Thus, all complexes KSCN·1a–g are assumed to
form plastic crystalline phases.
Presumably, the pairing thiocyanate anion induces the for-
mation of channel-like adducts by means of K–SCN–K
bridges, thus leading to a high degree of order (Scheme 2).
The p–p stacking between the aryl moieties would further
increase the intracolumnar order. Such bridging properties
of thiocyanates are well known in supramolecular chemis-
try[29] and have been studied by X-ray crystallography[29] and
capillary zone electrophoresis.[30]
Figure 7. Mesophase stabilities the complexes a) KBF4·1, b) KPF6·1, and
c) KSCN·1 upon first cooling. In the case of KPF6·1a,b and KSCN·1a–f,
X-ray diffraction reveals a highly ordered phase which was assigned as
&
plastic crystalline phase. For KPF6·1c, second heating is shown. Key:
=
&
crystal, =Col, & =plastic.
KBF4·1d–g with chain lengths C9–C12 formed mesophases
between 68 and 818C upon first cooling. The DSC curves
reveal an additional crystal-to-crystal transition in the tem-
perature range 11–408C. The heating cycles indicate mono-
tropic behavior of derivatives KBF4·1d–g. Upon cooling
from the isotropic liquid, tetrafluoroborate complexes of
1d–g gave fan-shaped textures, as exemplified by 1g in Fig-
ure 8a.
The DSC curves of complexes NH4PF6·1b–g revealed
monotropic mesophases for all derivatives between 48 and
1388C. Complexes NH4PF6·1e,g showed a glass to meso-
phase transition at 63 and 528C, respectively, upon second
heating.
Figure 7b reveals that all KPF6-complexed crown ethers
1a–g formed (meso)phases, whereby KPF6 induced also a
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S. Laschat et al.
from overlapping reflections of the alkyl chains in their liq-
uidlike state and of the disordered stacking of the aromatic
units within the same column.[31,32]
The X-ray diffraction pattern and SAXS profile of the
liquid-crystalline phase of complex KF·1 f is shown in Fig-
ure 10c and d. At 728C, three distinct maxima were ob-
served at small scattering angles. The corresponding d spac-
p
ings of 32.7, 18.8, and 16.4 ꢆ match the ratio of 1:1/ 3:1/2.
Indexing the peaks as (10), (11), and (20), the ratio is consis-
tent with values for a 2D hexagonal lattice with a=37.8 ꢆ.
Also, KBr induced a mesophase change from rectangular
columnar (free 1 f) to hexagonal columnar (Colh) as ob-
served for KBr·1 f. Colh mesophases were also observed for
complexes KBF4·1e, KBr·1e, and KCl·1e with hard anions
(see the Supporting Information).
Scheme 2. Possible SCNꢀ-induced formation of channel-like adducts of
complex KSCN·1.
For KI·1 f, five intense reflections were observed in the
small-angle region, which were indexed as (20), (21), (31),
(12), and (41), respectively (Figure 10f). As the values of d
spacing derived from the angular positions of the reflections
are consistent with neither a hexagonal nor a lamellar struc-
ture, the presence of a rectangular unit cell was concluded.
By comparing the SAXS profiles, it is obvious that 1 f and
complex KI·1 f show different rectangular symmetries. In
the case of 1 f, the (11) and (20) reflections were observed
very close to each other, whereas in the SAXS profile of
KI·1 f the (11) reflection is absent. From X-ray scattering ex-
periments rectangular columnar phases can also be deduced
for 1g, KCl·1 f, KBF4·1 f, KI·1e, and KPF6·1b,f (see the Sup-
porting Information).
However, it is difficult to distinguish in all these cases be-
tween the three most common symmetries P21/a, P2/a, and
C2/m observed for rectangular phases. Only in the case of
KPF6·1 f could the C2/m symmetry be excluded because the
(21) reflection with an odd sum of h+k was observed, which
is forbidden in this symmetry group.[33] In the other cases,
the reflections match the conditions for all three groups. As
P21/a and C2/m require two molecules in the unit cell,
whereas P2/a requires four molecules, the number of mole-
cules in the unit cell, Z, was calculated according to Equa-
tion (1).[34]
For complex NH4PF6·1d, fan-shaped textures were ob-
served by POM (Figure 9). However, during the heating
cycle, gas evolution by liberation of ammonia was observed.
Figure 9. Texture of complex NH4PF6·1d as seen between crossed polariz-
ers at 1308C upon cooling (cooling rate 10 Kminꢀ1, magnification ꢅ200).
Presumably, heating caused decomposition of the complex.
To verify this hypothesis, a thermogravimetric analysis
(TGA) of complexes NH4PF6·1d–f was carried out. The
sample was heated (20 Kminꢀ1) under an atmosphere of dry
nitrogen and the mass of the sample was recorded versus
temperature. Loss of mass of NH4PF6·1d–f began around
the clearing points, which is in accordance with observations
made under polarizing optical microscopy.
1NAAh
Mr
X-ray diffraction: The preliminary assignments of the differ-
ent mesophases based on characteristic textures (Figures 5
and 8) were supported by X-ray diffraction measurements.
The X-ray diffraction pattern and the corresponding small-
angle X-ray scattering (SAXS) profile of free crown ether
1 f (Figure 10a and b) confirmed the formation of a colum-
nar phase.
At 738C, two intense maxima being associated with d
values of 36.6 and 31.7 ꢆ and some weaker reflections (d
values of the most intensive peaks 19.1, 15.8, 12.9, 12.2, and
9.6 ꢆ; Table 1) were detected in the small-angle regime (Fig-
ure 10b), which originate from long-range intercolumnar or-
dering. These peaks were indexed as (11), (20), (31), (42),
(33), and (53), assuming a 2D rectangular lattice with pa-
rameters a=63.5 and b=45.0 ꢆ (Table 1). The broad scat-
tering halos in the wide-angle regime (Figure 10a) result
ð1Þ
Z ¼
in which 1=density of the complex (assuming 1=1 gcmꢀ3
as a typical approximation for organic substances), NA =
Avogadroꢄs constant, A=columnar cross section, and h=
height of the columnar unit, which can be obtained from the
diffuse scattering in the wide-angle region that originates
from the core–core interactions.
Applying Equation (1) to 1 f, 1g, and complexes KCl·1 f
and KBF4·1 f yielded Z=3.6–4.0 (Table 2). Thus four mole-
cules are placed in one unit cell and the symmetry of the
rectangular mesophase was identified as P2/a (Table 2).
To further confirm whether four molecules can fit into the
respective unit cell, the lattice parameters were compared
with the molecular dimensions derived from simple molecu-
9536
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ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 9530 – 9542

Dibenzo[18]crown-6 Derivatives
FULL PAPER
The formation of hexagonal
columnar mesophases was ob-
served for potassium complexes
KF·1 f, KCl·1e, KBr·1e,f, and
KBF4·1e with hard anions, in
which ion pairing is negligible
as proposed from NMR spec-
troscopy studies of the series
KX·1 f (see above). Considering
also the previous findings from
Swager and Lai et al.[36,37] that
weaker core interactions are
necessary for the formation of
hexagonal columnar mesophas-
es than for rectangular colum-
nar mesophases, we conclude
quite weak interactions be-
tween the cores of the mole-
cules, which result in hexagonal
columnar mesophases with rela-
tively small mesophase widths.
In contrast, the complexes
KI·1e, KI·1 f, and KPF6·1b,f ex-
hibit
columnar
rectangular
phases with broad mesophase
widths as expected from the
strong core interactions, which
agree with the NMR spectros-
copy experiments. The bridging
thiocyanate anion leads to com-
plexes with highly ordered plas-
tic phases. Thus, the counterion
determines the strengths of in-
tracolumnar interaction through
ion pairing. Complexes with
weak ion pairing properties fa-
vored the formation of hexago-
nal
columnar
mesophases,
whereas complexes derived
from strongly ion-pairing salts
preferred rectangular columnar
mesophase formation. Very
strong ion pairs lead to plastic
phases.
Figure 10. X-ray diffraction patterns (wide angle scattering, WAXS) and the corresponding small-angle scatter-
ing (SAXS) profiles of the liquid-crystalline phases of (a,b) free crown ether derivative 1 f at 738C; (c,d) com-
plex KF·1 f at 728C; and (e,f) complex KI·1 f at 1248C.
Figure 11 summarizes the
mesophase stabilities of crown
lar modeling (Chem3D).[35] For example, KCl·1 f was calcu-
lated to be 18ꢅ45 ꢆ in size so that four molecules can fit
into the unit cell with lattice parameters a=65 and b=44 ꢆ.
The molecules are assumed to pack over each other in a par-
allel manner as observed earlier for a similar system.[13]
In case of KF·1e, KI·1e,f, and KPF6·1b,f, calculation of Z
did not clarify the symmetry of the mesophases because the
number of molecules in the cell was calculated to be three
or six. However, it must be mentioned that an assumed den-
sity of 1.00 for the examined systems is a very rough esti-
mate. Additional density measurements might help to clarify
unambiguously the precise symmetry group in these cases.
ether 1 f and complexed 1 f with various salts and shows that
hard anions destabilize columnar mesophases, whereas soft
anions stabilize them.
Conclusion
Crown ethers are an important bridge between supramolec-
ular chemistry and materials chemistry and give access to
functional materials with properties that are sensitive to
chemical stimuli. To get a more detailed understanding of
Chem. Eur. J. 2009, 15, 9530 – 9542
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
9537

S. Laschat et al.
Table 1. X-ray diffraction data for uncomplexed 1 f and its complexes
MX·1 f.[a]
Table 2. Number of molecules, Z, in the unit cells calculated according
to Equation (1).
Compound
Mesophase
Lattice
d spacing [ꢆ]
Miller
Compound
Calcd size of 1 [ꢆ]
Z
Symmetry
spacing [ꢆ]
obsd (calcd)
indices
1 f
1g
KCl·1 f
KBF4·1 f
18ꢅ45
20ꢅ47
18ꢅ45
18ꢅ45
3.9
4.0
3.7
3.6
P2/a
P2/a
P2/a
P2/a
1 f
Colr at 738C
P2/a[b]
a=63.5
b=45.0
36.6 (36.7)
31.7 (31.7)
22.2 (22.5)
19.1 (19.2)
18.3 (18.4)
15.8 (15.9)
14.7 (14.6)
12.9 (13.0)
12.2 (12.2)
11.3 (11.3)
9.6 (9.7)
(11)
(20)
(02)
(31)
(22)
(40)
(13)
(42)
(33)
(04)
(53)
–
4.6 (halo)
32.7 (32.7)
18.8 (18.9)
16.4 (16.4)
4.6 (halo)
36.2 (36.2)
32.5 (32.5)
22.2 (21.8)
19.1 (19.3)
18.2 (18.1)
12.8 (13.0)
12.1 (12.4)
4.5 (halo)
32.7 (32.7)
18.9 (18.9)
16.4 (16.4)
4.5 (halo)
33.1 (33.1)
24.6 (24.6)
19.0 (18.9)
17.8 (17.7)
14.9 (15.0)
4.6 (halo)
37.0 (37.0)
33.0 (33.0)
18.4 (18.5)
16.6 (16.5)
12.9 (13.0)
12.2 (12.1)
4.7 (halo)
32.6 (32.6)
29.6 (29.6)
24.1 (24.1)
22.5 (22.3)
20.9 (20.8)
16.6 (16.3)
14.6 (14.8)
4.7 (halo)
–
KF·1 f
Colh at 728C
P6/mmm
a=37.8
(10)
(11)
(20)
–
(11)
(20)
(02)
(31)
(22)
(42)
(51)
–
(10)
(11)
(20)
–
(20)
(21)
(31)
(12)
(41)
–
(20)
(11)
(02)
(22)
(42)
(13)
–
(20)
(21)
(22)
(13)
(31)
(40)
(42)
–
KCl·1 f
Colr at 758C
P2/a[b]
a=64.9
b=43.6
Figure 11. Mesophase stabilities of crown ether 1 f and complexed 1 f
KBr·1 f
KI·1 f
Colh at 778C
P6/mmm
a=37.8
&
&
with various salts. Key: =crystal, =Col, & =DL.
Colr at 1248C
a=66.1
b=36.8
type of mesophase can be changed by choosing a particular
salt. Although 1, KF·1, KCl·1, KBr·1, KI·1, KBF4·1, and
KPF6·1 show columnar mesophases, NH4PF6·1 displays a dis-
cotic lamellar arrangement of the molecules, and the pairing
soft thiocyanate anion introduces a high degree of order
into the complexes KSCN·1, thus resulting in plastic phases
instead of columnar mesophases (see the Supporting Infor-
mation).
KBF4·1 f
Colr at 748C
P2/a[b]
a=73.9
b=36.9
1H and 13C NMR spectroscopic results indicate the pres-
ence of ion pairs in KBr·1, KI·1, KSCN·1, KPF6·1, and
NH4PF6·1. These observations are in good agreement with
the increased clearing points of the complexes as compared
to the uncomplexed crown ethers 1 so that NMR spectros-
copy can be used for the prediction of the mesomorphic
properties of MX·1. The findings further show that the
liquid-crystalline properties can be tailored more effectively
by metal salts than by the variation of alkyl-chain lengths.
Attempts to utilize this salt effect for other liquid crystals
are currently in progress.
KPF6·1 f
Colr at 1058C
a=65.2
b=71.2
KSCN·1 f
NH4PF6·1 f
P
plastic crystal
–
–
–
ACHTUNGTRENNUNG
DL at 1208C
34.8
17.4
ACHTUNGTRENNUNG
[a] Further X-ray diffraction data as well as WAXS pattern for discotic
lamellar (DL) and plastic (P) phases observed in this work are shown in
the Supporting Information. [b] Deduced from Equation (1).
Experimental Section
General methods: Melting points were measured using a Mettler Toledo
DSC822 and are uncorrected. NMR spectra were recorded using Bruker
Avance 300 and Avance 500 spectrometers. FTIR spectra were recorded
using a Bruker Vektor22 spectrometer with an MKII Golden Gate Single
Reflection Diamant ATR system. Mass spectra were recorded using a
Finnigan MAT 95 and a Varian MAT 711 apparatus. MALDI-TOF spec-
tra were recorded using a Bruker Reflex IV spectrometer with a nitrogen
laser (l=337 nm); software: XACQ 4.0.4 and XMASS/XTOF 5.1.0.[38]
complexation-induced effects, we synthesized and investigat-
ed
a series of crown ether complexes KX·1a–g and
NH4PF6·1b–g. Hard anions such as fluoride, chloride, and
tetrafluoroborate destabilize columnar mesophases, whereas
soft anions such as iodide and bridging anions like hexa-
fluorophosphate stabilize mesophases. Furthermore, the
9538
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ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 9530 – 9542

Dibenzo[18]crown-6 Derivatives
FULL PAPER
X-ray powder experiments were performed using a Bruker Nanostar;
software: SAXS 4.1.26.[39] The samples were kept in Hilgenberg glass ca-
pillaries of 0.7 mm outside diameter in a temperature-controlled heating
stage (ꢂ18C). A monochromatic CuKa1 beam (l=1.5405 ꢆ) was obtained
using a ceramic tube generator (1500 W) with cross-coupled Gçbel mir-
rors as the monochromator. The diffraction patterns were recorded using
a real-time 2D-detector (HI-STAR, Bruker). The calibration of the pat-
terns occurred with the powder pattern of Ag-Behenate. Differential
134.6 (C-4, C-4’, C-5, C-5’, C-1’’), 147.6 (C-1, C-1’, C-2, C-2’), 148.0,
148.5 ppm (C-3’’, C-4’’); FTIR (ATR): v˜ =2955, 2920, 2852 (vs), 1497 (s),
1467 (m), 1456 (m), 1245 (vs), 1197 (m), 1136 (m), 1066 (m), 1024 (m),
861 (w), 803 (m), 606 cmꢀ1 (w); MS (MALDI-TOF): m/z: calcd for
[C132H216O14K+]: 2064.6; found: 2064.9.
4,4’,5,5’-Tetrakis[3’’,4’’-bis(undecyloxy)phenyl]dibenzo[18]crown-6 potas-
sium chloride complex (KCl·1 f): Colorless solid; 1H NMR (CD2Cl2,
300 MHz): d=0.89–0.94 (m, 24H; CH3), 1.31–1.53 (m, 128H; O
(CH2)8CH3), 1.60–1.69 (m, 8H; OCH2CH2A(CH2)8CH3), 1.75–1.84 (m, 8H;
OCH2CH2A(CH2)8CH3), 3.69 (t, J=6.6 Hz, 8H; OCH2A(CH2)9CH3), 3.95 (t,
J=6.6 Hz, 8H; OCH2A(CH2)9CH3), 4.02 (m, 8H; H-b), 4.25 (m, 8H; H-a),
ACHTUNGTRENNUNG(CH2)2-
scanning calorimetry (DSC) was performed using
a Mettler Toledo
A
CHTUNGTRENNUNG
DSC822, and polarizing optical microscopy (POM) using an Olympus
BX50 polarizing microscope combined with a Linkam LTS350 hot stage
and a Linkam TP93 central processor.
C
CHTUNGTRENNUNG
CTHUNGTRENNUNG
6.61 (d, J=1.5 Hz, 4H; H-2’’), 6.75 (dd, J=8.3, 1.5 Hz, 4H; H-6’’), 6.80
(d, J=8.3 Hz, 4H; H-5’’), 6.94 ppm (s, 4H; H-3, H-3’, H-6, H-6’);
13C NMR (CD2Cl2, 75 MHz): d=14.0 (CH3), 22.8, 26.18, 26.21, 29.4,
29.49, 29.52, 29.58, 29.62, 29.79, 29.82, 29.84, 29.9, 32.06, 32.08 (OCH2-
The spectroscopic data of complexes KI·1a–e were in accordance with
those in the literature,[40] and the data of complexes MX·1a–e are sum-
marized in the Supporting Information.
ACHUTNGRENUN(G CH2)9CH3), 68.5 (C-a), 69.3, 69.4 (OCH2AHCUTNGTRENN(GUN CH2)9CH3), 69.9 (C-b), 113.5
4,4’,5,5’-Tetrakis[3’’,4’’-bis(undecyloxy)phenyl]dibenzo[18]crown-6 (1 f):
Yield: 82%; 1H NMR (CDCl3, 300 MHz): d=0.86–0.90 (m, 24H; CH3),
(C-5’’), 115.0 (C-3, C-3’, C-6, C-6’), 116.6 (C-2’’), 122.0 (C-6’’), 133.1,
134.6 (C-4, C-4’, C-5, C-5’, C-1’’), 147.5 (C-1, C-1’, C-2, C-2’), 148.0,
148.5 ppm (C-3’’, C-4’’); FTIR (ATR): v˜ =2957 (w), 2921, 2852 (vs), 1497
(s), 1467 (m), 1245 (vs), 1198 (m), 1136 (m), 1066 (s), 1020 (s), 862 (w),
800 (s), 613 cmꢀ1 (m); MS (MALDI-TOF): m/z: calcd for [C132H216O14K+]:
2064.6; found: 2065.4.
1.26–1.50 (m, 128H; O
(CH2)8CH3), 1.74–1.83 (m, 8H; OCH2CH
8H; OCH2A(CH2)9CH3), 3.94 (t, J=6.7 Hz, 8H; OCH HCTUNGTRENNUNG
ACHTUNGTRENNUNG(CH2)2ACHTUGNTRENNNUG
(CH2)8CH3), 1.59–1.69 (m, 8H; OCH2CH2-
2A(CH2)8CH3), 3.67 (t, J=6.7 Hz,
2A(CH2)9CH3), 4.00
G
CHTUNGTRENNUNG
T
(m, 8H; H-b), 4.24 (m, 8H; H-a), 6.57 (d, J=1.7 Hz, 4H; H-2’’), 6.69
(dd, J=8.2, 1.7 Hz, 4H; H-6’’), 6.74 (d, J=8.2 Hz, 4H; H-5’’), 6.94 ppm
(s, 4H; H-3, H-3’, H-6, H-6’); 13C NMR (CD2Cl2, 75 MHz): d=14.0
(CH3), 22.8, 26.1, 26.2, 29.3, 29.47, 29.50, 29.54, 29.6, 29.76, 29.80, 29.81,
4,4’,5,5’-Tetrakis[3’’,4’’-bis(undecyloxy)phenyl]dibenzo[18]crown-6 potas-
sium bromide complex (KBr·1 f): Pale brown solid; 1H NMR (CD2Cl2,
29.83, 32.0, 32.1 (OCH
ACHTUNGTRENNUNG
2ACTHNUGTREN(NUNG CH2)9CH3), 68.6 (C-a), 69.2, 69.3 (OCH2-
300 MHz): d=0.89–0.93 (m, 24H; CH3), 1.30–1.52 (m, 128H; O
(CH2)8CH3), 1.59–1.68 (m, 8H; OCH2CH2A(CH2)8CH3), 1.74–1.84 (m, 8H;
OCH2CH2A(CH2)8CH3), 3.67 (t, J=6.6 Hz, 8H; OCH2A(CH2)9CH3), 3.95 (t,
J=6.6 Hz, 8H; OCH2A(CH2)9CH3), 4.17 (m, 8H; H-b), 4.28 (m, 8H; H-a),
6.59 (d, J=1.7 Hz, 4H; H-2’’), 6.75 (dd, J=8.2, 1.7 Hz, 4H; H-6’’), 6.80
(d, J=8.2 Hz, 4H; H-5’’), 6.95 ppm (s, 4H; H-3, H-3’, H-6, H-6’);
13C NMR (CD2Cl2, 75 MHz): d=14.0 (CH3), 22.8, 26.1, 26.2, 29.3, 29.4,
ACHTUNGTRENNUNG(CH2)2-
U
CHTUNGTRENNUNG
(C-2’’), 122.0 (C-6’’), 133.0, 134.5 (C-4, C-4’, C-5, C-5’, C-1’’), 147.6, 147.9
(C-4’’, C-3’’), 148.5 ppm (C-1, C-1’, C-2, C-2’); FTIR (ATR): v˜ =2920,
2852 (vs), 1497 (s), 1468 (m), 1456 (m), 1245 (vs), 1199 (m), 1137 (m),
1066 (w), 862 (w), 806 cmꢀ1 (w); MS (MALDI-TOF): m/z: calcd for
[C132H216O14+]: 2025.6; found: 2025.1; elemental analysis calcd (%) for
C132H216O14 (2025.6): C 78.21, H 10.74; found: C 77.96, H 10.74.
G
CHTUNGTRENNUNG
CTHUNGTRENNUNG
29.47, 29.52, 29.6, 29.7, 29.78, 29.83, 32.0, 32.1 (OCH
2ACHTUNGTNERN(UNG CH2)9CH3), 67.7,
69.1 (C-a, C-b), 69.3 (OCH2A(CH2)9CH3), 113.3 (C-5’’), 113.5 (C-3, C-3’, C-
CTHUNGTRENNUNG
4,4’,5,5’-Tetrakis[3’’,4’’-bis(dodecyloxy)phenyl]dibenzo[18]crown-6 (1g):
Yield: 83%; 1H NMR (CD2Cl2, 300 MHz): d=0.89–0.93 (m, 24H; CH3),
6, C-6’), 116.5 (C-2’’), 122.0 (C-6’’), 133.3, 134.2 (C-4, C-4’, C-5, C-5’, C-
1’’), 146.1 (C-1, C-1’, C-2, C-2’), 148.1, 148.5 ppm (C-3’’, C-4’’); FTIR
(ATR): v˜ =2955 (w), 2921, 2852 (vs), 1498 (s), 1467 (m), 1456 (m), 1244
(vs), 1197 (m), 1134 (m), 1066 (m), 1023 (m), 806 (w), 801 (w), 615 cmꢀ1
(w); MS (MALDI-TOF): m/z: calcd for [C132H216O14K+]: 2064.6; found:
2064.8.
1.30–1.52 (m, 144H; O
(CH2)9CH3), 1.74–1.83 (m, 8H; OCH2CH
8H; OCH2A(CH2)10CH3), 3.94 (t, J=6.6 Hz, 8H; OCH HCTUNGTRENNUNG
ACHTUNGTRENNUNG(CH2)2ACHTUGNTRENNNUG
(CH2)9CH3), 1.59–1.68 (m, 8H; OCH2CH2-
2A(CH2)9CH3), 3.68 (t, J=6.6 Hz,
2A(CH2)10CH3), 4.00–
E
CHTUNGTRENNUNG
N
4.02 (m, 8H; OCH2CH2O), 4.23–4.26 (m, 8H; OCH2CH2O), 6.60 (d, J=
1.8 Hz, 4H; H-2’’), 6.75 (dd, J=8.2, 1.8 Hz, 4H; H-6’’), 6.79 (d, J=
8.3 Hz, 4H; H-5’’), 6.94 ppm (s, 4H; H-3, H-3’, H-6, H-6’); 13C NMR
(CD2Cl2, 75 MHz): d=14.0 (CH3), 22.8, 26.15, 26.19, 29.3, 29.47, 29.50,
4,4’,5,5’-Tetrakis[3’’,4’’-bis(undecyloxy)phenyl]dibenzo[18]crown-6 potas-
1
sium iodide complex (KI·1 f): Brown solid; H NMR (CD2Cl2, 300 MHz):
29.55, 29.60, 29.77, 29.81, 29.85, 29.88, 32.0, 32.1 (OCH
2ACHTUGNERTN(NUNG CH2)10CH3), 68.7
d=0.89–0.93 (m, 24H; CH3), 1.31–1.53 (m, 128H; O
1.59–1.68 (m, 8H; OCH2CH2A(CH2)8CH3), 1.74–1.84 (m, 8H; OCH2CH2-
(CH2)8CH3), 3.67 (t, J=6.6 Hz, 8H; OCH2A(CH2)9CH3), 3.95 (t, J=6.6 Hz,
8H; OCH2A(CH2)9CH3), 4.28 (m, 8H; H-b), 4.30 (m, 8H; H-a), 6.59 (d,
CAHUTGTNREN(NGU CH2)2ACHTUGNTRNE(NUGN CH2)8CH3),
(OCH2CH2O), 69.26, 69.33 (OCH2A(CH2)10CH3), 70.0 (OCH2CH2O), 113.4
CTHUNGTRENNUNG
CTHUNGTRENNUNG
(C-5’’), 115.3 (C-3, C-3’, C-6, C-6’), 116.5 (C-2’’), 122.0 (C-6’’), 133.1,
134.6 (C-4, C-4’, C-5, C-5’, C-1’’), 147.7, 147.9 (C-3’’, C-4’’), 148.5 ppm (C-
1, C-1’, C-2, C-2’); FTIR (ATR): v˜ =2955, 2920, 2851 (vs), 1500 (m), 1468
(m), 1248 (s), 1200 (m), 1137 (m), 1068 (w), 861 (w), 803 (w), 721 cmꢀ1
(w); MS (MALDI-TOF): m/z: calcd for [C140H232O14+]: 2137.8; found:
2138.8; elemental analysis calcd (%) for C140H232O14 (2133.7): C 78.60, H
10.93; found: C 78.43, H 10.83.
A
CHTUNGTRENNUNG
CTHUNGTRENNUNG
J=1.7 Hz, 4H; H-2’’), 6.76 (dd, J=8.2, 1.7 Hz, 4H; H-6’’), 6.81 (d, J=
8.2 Hz, 4H; H-5’’), 6.96 ppm (s, 4H; H-3, H-3’, H-6, H-6’); 13C NMR
(CD2Cl2, 75 MHz): d=14.0 (CH3), 22.8, 26.1, 26.2, 29.3, 29.45, 29.49,
29.53, 29.6, 29.7, 29.79, 29.80, 29.81, 32.01, 32.03 (OCH
2ACHTUNGTNERN(UNG CH2)9CH3), 67.6,
69.0 (C-a, C-b), 69.3 (OCH2A(CH2)9CH3), 113.3 (C-5’’), 113.4 (C-3, C-3’, C-
CTHUNGTRENNUNG
6, C-6’), 116.5 (C-2’’), 122.0 (C-6’’), 133.4, 134.1 (C-4, C-4’, C-5, C-5’, C-
1’’), 145.9 (C-1, C-1’, C-2, C-2’), 148.1, 148.5 ppm (C-3’’, C-4’’); FTIR
(ATR): v˜ =2920, 2852 (vs), 1497 (s), 1467 (s), 1456 (s), 1243 (vs), 1195
(s), 1124 (s), 1065 (m), 959 (w), 862 (w), 806 (w), 798 (w), 612 cmꢀ1 (w);
MS (MALDI-TOF): m/z: calcd for [C132H216O14K+]: 2064.6; found:
2065.6.
General procedure for the complexation: A solution of the respective 1
(18.7 mmol) in CH2Cl2 (2.5 mL) was added to a solution of the respective
salt (28.0 mmol) in MeOH (2.5 mL) and the reaction mixture stirred over-
night at 408C. After evaporation of the solvent, the residue was taken up
in CH2Cl2, filtered through paper, concentrated in vacuo, and dried
under high vacuum to yield the complexes MX·1 quantitatively.
4,4’,5,5’-Tetrakis[3’’,4’’-bis(undecyloxy)phenyl]dibenzo[18]crown-6 potas-
sium thiocyanate complex (KSCN·1 f): Pale brown solid; 1H NMR
(CD2Cl2, 300 MHz): d=0.89–0.93 (m, 24H; CH3), 1.31–1.53 (m, 128H;
4,4’,5,5’-Tetrakis[3’’,4’’-bis(undecyloxy)phenyl]dibenzo[18]crown-6 potas-
sium fluoride complex (KF·1 f): Colorless solid; 1H NMR (CD2Cl2,
300 MHz): d=0.89–0.94 (m, 24H; CH3), 1.31–1.53 (m, 128H; O
(CH2)8CH3), 1.59–1.69 (m, 8H; OCH2CH2A(CH2)8CH3), 1.75–1.84 (m, 8H;
OCH2CH2A(CH2)8CH3), 3.69 (t, J=6.6 Hz, 8H; OCH2A(CH2)9CH3), 3.95 (t,
J=6.6 Hz, 8H; OCH2A(CH2)9CH3), 4.02 (m, 8H; H-b), 4.25 (m, 8H; H-a),
ACHTUGNTERN(NUNG CH2)2-
O
A
E
2ACHTUNGTRENN(NUG CH2)8CH3), 1.75–1.84
A
CHTUNGTRENNUNG
CTHUNGTRENNUNG
C
CHTUNGTRENNUNG
A
CHTUNGTRENNUNG
CHTUNGTRENNUNG
6.61 (d, J=1.7 Hz, 4H; H-2’’), 6.75 (dd, J=8.3, 1.7 Hz, 4H; H-6’’), 6.80
(d, J=8.3 Hz, 4H; H-5’’), 6.94 ppm (s, 4H; H-3, H-3’, H-6, H-6’);
13C NMR (CD2Cl2, 75 MHz): d=14.0 (CH3), 22.8, 26.18, 26.21, 29.4,
29.49, 29.52, 29.57, 29.62, 29.79, 29.82, 29.84, 32.05, 32.07 (OCH2-
b), 4.31 (m, 8H; H-a), 6.60 (d, J=1.7 Hz, 4H; H-2’’), 6.76 (dd, J=8.2,
1.7 Hz, 4H; H-6’’), 6.81 (d, J=8.2 Hz, 4H; H-5’’), 6.97 ppm (s, 4H; H-3,
H-3’, H-6, H-6’); 13C NMR (CD2Cl2, 75 MHz): d=14.0 (CH3), 22.8, 26.1,
26.2, 29.3, 29.4, 29.47, 29.52, 29.6, 29.7, 29.77, 29.79, 32.00, 32.03 (OCH2-
A
H
N
2ACHTUNGTRENNUN(G CH2)9CH3), 113.3 (C-5’’),
Chem. Eur. J. 2009, 15, 9530 – 9542
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
9539

S. Laschat et al.
C-4’, C-5, C-5’, C-1’’), 145.8 (C-1, C-1’, C-2, C-2’), 148.1, 148.5 ppm (C-3’’,
C-4’’); FTIR (ATR): v˜ =2955 (w), 2921, 2852 (vs), 2051 (w), 1497 (s),
1467 (m), 1456 (m), 1243 (vs), 1196 (m), 1124 (m), 1066 (w), 863 (w), 800
(m), 615 cmꢀ1 (m); MS (MALDI-TOF): m/z: calcd for [C132H216O14K+]:
2064.6; found: 2063.7.
122.0 (C-6’’), 133.0, 134.6 (C-4, C-4’, C-5, C-5’, C-1’’), 147.4 (C-1, C-1’, C-
2, C-2’), 147.9, 148.5 ppm (C-3’’, C-4’’); FTIR (ATR): v˜ =2920, 2852 (vs),
1498 (s), 1467 (m), 1245 (vs), 1198 (m), 1136 (m), 1066 (w), 1024 (w), 960
(w), 862 (w), 799 cmꢀ1 (w); MS (MALDI-TOF): m/z: calcd for
[C140H232O14K+]: 2176.7; found: 2178.9; elemental analysis calcd (%) for
C140H232FKO14·MeOH (2227.7): C 75.96, H 10.76; found: C 75.87, H
10.64.
4,4’,5,5’-Tetrakis[3’’,4’’-bis(undecyloxy)phenyl]dibenzo[18]crown-6 potas-
sium hexafluorophosphate complex (KPF6·1 f): Colorless solid; 1H NMR
(CD2Cl2, 300 MHz): d=0.87–0.92 (m, 24H; CH3), 1.29–1.51 (m, 128H;
4,4’,5,5’-Tetrakis[3’’,4’’-bis(dodecyloxy)phenyl]dibenzo[18]crown-6 potas-
sium chloride complex (KCl·1g): Colorless solid; 1H NMR (CD2Cl2,
O
G
R
2ACHTUNGTRENN(NUG CH2)8CH3), 1.73–1.82
E
300 MHz): d=0.88–0.92 (m, 24H; CH3), 1.29–1.49 (m, 144H; O
(CH2)9CH3), 1.58–1.68 (m, 8H; OCH2CH2A(CH2)9CH3), 1.74–1.83 (m, 8H;
OCH2CH2A(CH2)9CH3), 3.67 (t, J=6.6 Hz, 8H; OCH2A(CH2)10CH3), 3.94
(t, J=6.6 Hz, 8H; OCH2A(CH2)10CH3), 4.03 (m, 8H; OCH2CH2O), 4.25
ACHTUNGTRENNUNG(CH2)2-
A
U
A
CHTUNGTRENNUNG
b), 4.28 (m, 8H; H-a), 6.57 (d, J=1.8 Hz, 4H; H-2’’), 6.74 (dd, J=8.3,
1.8 Hz, 4H; H-6’’), 6.79 (d, J=8.3 Hz, 4H; H-5’’), 6.96 ppm (s, 4H; H-3,
H-3’, H-6, H-6’); 13C NMR (CD2Cl2, 75 MHz): d=14.0 (CH3), 22.8, 26.15,
26.19, 29.3, 29.47, 29.50, 29.54, 29.6, 29.76, 29.80, 29.81, 29.83, 32.0, 32.1
C
CHTUNGTRENNUNG
CTHUNGTRENNUNG
(m, 8H; OCH2CH2O), 6.59 (d, J=1.8 Hz, 4H; H-2’’), 6.74 (dd, J=8.3,
1.8 Hz, 4H; H-6’’), 6.79 (d, J=8.3 Hz, 4H; H-5’’), 6.93 ppm (s, 4H; H-3,
H-3’, H-6, H-6’); 13C NMR (CD2Cl2, 75 MHz): d=14.0 (CH3), 22.8, 26.15,
26.18, 29.3, 29.47, 29.50, 29.54, 29.6, 29.76, 29.80, 29.84, 29.9, 32.0 (OCH2-
(OCH2ACHTUNGTRENNUNG(CH2)9CH3), 67.4, 68.7 (C-a, C-b), 69.3 (OCH2HCAUTNGTREN(NUGN CH2)9CH3), 113.3
(C-5’’), 113.4 (C-3, C-3’, C-6, C-6’), 116.5 (C-2’’), 122.0 (C-6’’), 133.5,
134.1 (C-4, C-4’, C-5, C-5’, C-1’’), 145.8 (C-1, C-1’, C-2, C-2’), 148.2,
148.6 ppm (C-3’’, C-4’’); FTIR (ATR): v˜ =2921, 2852 (vs), 1496 (s), 1467
(m), 1456 (m), 1244 (vs), 1195 (m), 1124 (m), 1067 (w), 960 (w), 840 (vs),
803 (s), 613 (w), 558 cmꢀ1 (m); MS (MALDI-TOF): m/z: calcd for
[C132H216O14K+]: 2064.6; found: 2064.2.
ACHUNTRGENUN(G CH2)10CH3), 68.4 (OCH2CH2O), 69.2, 69.3 (OCH2CAHUTNGTREN(NUGN CH2)10CH3), 69.8
(OCH2CH2O), 113.4 (C-5’’), 114.7 (C-3, C-3’, C-6, C-6’), 116.5 (C-2’’),
122.0 (C-6’’), 133.0, 134.5 (C-4, C-4’, C-5, C-5’, C-1’’), 147.4 (C-1, C-1’, C-
2, C-2’), 147.9, 148.5 ppm (C-3’’, C-4’’); FTIR (ATR): v˜ =2958 (m), 2921
(vs), 2852 (vs), 1498 (s), 1468 (m), 1258, 1246 (vs), 1199 (m), 1136 (s),
1067 (s), 1020 (s), 862 (w), 798 cmꢀ1 (s); MS (MALDI-TOF): m/z: calcd
for [C140H232O14K+]: 2176.7; found: 2179.2.
4,4’,5,5’-Tetrakis[3’’,4’’-bis(undecyloxy)phenyl]dibenzo[18]crown-6 potas-
sium tetrafluoroborate complex (KBF4·1 f): Colorless solid; 1H NMR
(CD2Cl2, 300 MHz): d=0.89–0.93 (m, 24H; CH3), 1.31–1.52 (m, 128H;
4,4’,5,5’-Tetrakis[3’’,4’’-bis(dodecyloxy)phenyl]dibenzo[18]crown-6 potas-
sium bromide complex (KBr·1g): Pale brown solid; 1H NMR (CD2Cl2,
O
G
R
2ACHTUNGTRENN(NUG CH2)8CH3), 1.75–1.84
E
300 MHz): d=0.88–0.93 (m, 24H; CH3), 1.30–1.52 (m, 144H; O
(CH2)9CH3), 1.58–1.66 (m, 8H; OCH2CH2A(CH2)9CH3), 1.74–1.83 (m, 8H;
OCH2CH2A(CH2)9CH3), 3.67 (t, J=6.6 Hz, 8H; OCH2A(CH2)10CH3), 3.94
(t, J=6.6 Hz, 8H; OCH2A(CH2)10CH3), 4.13 (m, 8H; OCH2CH2O), 4.27
ACHTUNGTRENNUNG(CH2)2-
A
U
A
CHTUNGTRENNUNG
b), 4.25 (m, 8H; H-a), 6.60 (d, J=1.7 Hz, 4H; H-2’’), 6.75 (dd, J=8.3,
1.7 Hz, 4H; H-6’’), 6.79 (d, J=8.3 Hz, 4H; H-5’’), 6.94 ppm (s, 4H; H-3,
H-3’, H-6, H-6’); 13C NMR (CD2Cl2, 75 MHz): d=14.0 (CH3), 22.8, 26.1,
26.2, 29.3, 29.5, 29.58, 29.60, 29.75, 29.80, 29.81, 32.02, 32.04 (OCH2-
C
CHTUNGTRENNUNG
CTHUNGTRENNUNG
(m, 8H; OCH2CH2O), 6.59 (d, J=1.8 Hz, 4H; H-2’’), 6.75 (dd, J=8.3,
1.8 Hz, 4H; H-6’’), 6.79 (d, J=8.3 Hz, 4H; H-5’’), 6.94 ppm (s, 4H; H-3,
H-3’, H-6, H-6’); 13C NMR (CD2Cl2, 75 MHz): d=14.0 (CH3), 22.8, 26.15,
26.18, 29.3, 29.47, 29.50, 29.54, 29.6, 29.76, 29.80, 29.84, 29.9, 32.0 (OCH2-
ACHTUNGTRENNUNG(CH2)9CH3), 68.4 (C-a), 69.2, 69.3 (OCH2CAHTUNGTRENN(GUN CH2)9CH3), 69.8 (C-b), 113.4
(C-5’’), 114.8 (C-3, C-3’, C-6, C-6’), 116.5 (C-2’’), 122.0 (C-6’’), 133.0,
134.5 (C-4, C-4’, C-5, C-5’, C-1’’), 147.4 (C-1, C-1’, C-2, C-2’), 147.9,
148.5 ppm (C-3’’, C-4’’); FTIR (ATR): v˜ =2920, 2852 (vs), 1497 (s), 1468
(m), 1456 (m), 1244 (vs), 1198 (m), 1136 (m), 1067 (w), 804 (w), 802 (w),
617 cmꢀ1 (m); MS (MALDI-TOF): m/z: calcd for [C132H216O14K+]:
2064.6; found: 2064.4.
ACHUNTRGENUN(G CH2)10CH3), 68.0 (OCH2CH2O), 69.3, 69.3 (OCH2CAHUTNGTREN(NUGN CH2)10CH3), 69.4
(OCH2CH2O), 113.38 (C-5’’), 113.42 (C-3, C-3’, C-6, C-6’), 116.5 (C-2’’),
122.0 (C-6’’), 133.3, 134.3 (C-4, C-4’, C-5, C-5’, C-1’’), 148.0, 148.5 ppm
(C-3’’, C-4’’) (the signal for C-1, C-1’, C-2, C-2’ could not be observed);
FTIR (ATR): v˜ =2959, 2921, 2852 (s), 1498 (s), 1467 (m), 1259, 1245 (vs),
1197 (m), 1164 (m), 1090 (s), 1068 (s), 1017 (vs), 862 (w), 797 cmꢀ1 (vs);
MS (MALDI-TOF): m/z: calcd for [C140H232O14K+]: 2176.7; found:
2175.1.
4,4’,5,5’-Tetrakis[3’’,4’’-bis(undecyloxy)phenyl]dibenzo[18]crown-6 ammo-
nium hexafluorophosphate complex (NH4PF6·1 f): Colorless solid;
1H NMR (CD2Cl2, 300 MHz): d=0.89–0.93 (m, 24H; CH3), 1.31–1.53 (m,
128H; O
1.75–1.84 (m, 8H; OCH2CH
(CH2)9CH3), 3.95 (t, J=6.6 Hz, 8H; OCH
b), 4.32 (m, 8H; H-a), 6.59 (d, J=1.6 Hz, 4H; H-2’’), 6.75 (dd, J=8.3,
1.6 Hz, 4H; H-6’’), 6.80 (d, J=8.3 Hz, 4H; H-5’’), 6.97 ppm (s, 4H; H-3,
H-3’, H-6, H-6’); 13C NMR (CD2Cl2, 75 MHz): d=14.0 (CH3), 22.8, 26.16,
26.19, 29.3, 29.47, 29.50, 29.54, 29.55, 29.60, 29.76, 29.81, 29.82, 32.0, 32.1
(CH2)
R
(CH2)8CH3),
4,4’,5,5’-Tetrakis[3’’,4’’-bis(dodecyloxy)phenyl]dibenzo[18]crown-6 potas-
sium iodide complex (KI·1g): Brown solid; H NMR (CD2Cl2, 300 MHz):
1
G
G
N
d=0.88–0.92 (m, 24H; CH3), 1.30–1.51 (m, 144H; O
1.58–1.67 (m, 8H; OCH2CH2A(CH2)9CH3), 1.74–1.83 (m, 8H; OCH2CH2-
(CH2)9CH3), 3.67 (t, J=6.6 Hz, 8H; OCH2A(CH2)10CH3), 3.94 (t, J=
6.6 Hz, 8H; OCH2A(CH2)10CH3), 4.26 (m, 8H; OCH2CH2O), 4.30 (m, 8H;
CAHUTGTNREN(NGU CH2)2ACHTUGNTRNE(NUGN CH2)9CH3),
CHTUNGTRENNUNG
A
CHTUNGTRENNUNG
CTHUNGTRENNUNG
OCH2CH2O), 6.58 (d, J=1.7 Hz, 4H; H-2’’), 6.75 (dd, J=8.3, 1.7 Hz,
4H; H-6’’), 6.80 (d, J=8.3 Hz, 4H; H-5’’), 6.95 ppm (s, 4H; H-3, H-3’, H-
6, H-6’); 13C NMR (CD2Cl2, 75 MHz): d=14.0 (CH3), 22.8, 26.1, 26.2,
29.3, 29.46, 29.49, 29.54, 29.6, 29.76, 29.79, 29.83, 29.9, 32.0 (OCH2-
(OCH2ACHTUNGTRENNUNG(CH2)9CH3), 67.3, 69.3 (C-a, C-b), 69.3 (OCH2HCAUTNGTREN(NUGN CH2)9CH3), 113.4
(C-5’’), 113.9 (C-3, C-3’, C-6, C-6’), 116.5 (C-2’’), 122.0 (C-6’’), 133.7,
134.1 (C-4, C-4’, C-5, C-5’, C-1’’), 145.8 (C-1, C-1’, C-2, C-2’), 148.2,
148.6 ppm (C-3’’, C-4’’); FTIR (ATR): v˜ =3229 (w), 2921, 2852 (vs), 1498
(s), 1466 (m), 1456 (m), 1243 (vs), 1196 (m), 1132 (m), 1067 (w), 959 (w),
840 (vs), 806 (m), 721 (w), 611 (w), 558 cmꢀ1 (m); MS (MALDI-TOF):
m/z: calcd for [C132H216O14+]: 2025.6; found: 2025.4.
ACHUNTGERNUN(G CH2)10CH3), 67.6, 69.0 (OCH2CH2O), 69.3 (OCH2ACHTUNTGRENN(GUN CH2)10CH3), 113.4
(C-5’, C-3, C-3’, C-6, C-6’), 116.5 (C-2’’), 122.0 (C-6’’), 133.4, 134.1 (C-4,
C-4’, C-5, C-5’, C-1’’), 145.9 (C-1, C-1’, C-2, C-2’), 148.1, 148.5 ppm (C-3’’,
C-4’’); FTIR (ATR): v˜ =2958, 2922, 2852 (vs), 1497 (s), 1467 (m), 1386
(w), 1260, 1245 (vs), 1198 (m), 1066 (vs), 1021 (vs), 862 (w), 800 cmꢀ1
(vs); MS (MALDI-TOF): m/z: calcd for [C140H232O14K+]: 2176.7; found:
2174.8; elemental analysis calcd (%) for C140H232IKO14 (2305.3): C 72.94,
H 10.14; found: C 72.96, H 10.08.
4,4’,5,5’-Tetrakis[3’’,4’’-bis(dodecyloxy)phenyl]dibenzo[18]crown-6 potas-
sium fluoride complex (KF·1g): Colorless solid; 1H NMR (CD2Cl2,
300 MHz): d=0.88–0.92 (m, 24H; CH3), 1.30–1.49 (m, 144H; O
(CH2)9CH3), 1.58–1.67 (m, 8H; OCH2CH2A(CH2)9CH3), 1.74–1.83 (m, 8H;
OCH2CH2A(CH2)9CH3), 3.67 (t, J=6.6 Hz, 8H; OCH2A(CH2)10CH3), 3.94
(t, J=6.6 Hz, 8H; OCH2A(CH2)10CH3), 4.02 (m, 8H; OCH2CH2O), 4.25
A
CHTUNGTRENNUNG
R
4,4’,5,5’-Tetrakis[3’’,4’’-bis(dodecyloxy)phenyl]dibenzo[18]crown-6 potas-
sium thiocyanate complex (KSCN·1g): Pale brown solid; 1H NMR
(CD2Cl2, 300 MHz): d=0.86–0.90 (m, 24H; CH3), 1.27–1.50 (m, 144H;
CTHUNGTRENNUNG
(m, 8H; OCH2CH2O), 6.59 (d, J=1.6 Hz, 4H; H-2’’), 6.74 (dd, J=8.3,
1.6 Hz, 4H; H-6’’), 6.79 (d, J=8.3 Hz, 4H; H-5’’), 6.93 ppm (s, 4H; H-3,
H-3’, H-6, H-6’); 13C NMR (CD2Cl2, 75 MHz): d=14.0 (CH3), 22.8, 26.1,
26.2, 29.3, 29.46, 29.49, 29.53, 29.6, 29.75, 29.79, 29.83, 29.9, 32.0 (OCH2-
O
G
E
2ACHTUNGTRENN(NUG CH2)9CH3), 1.72–1.81
CTHUNGTRENNUNG
A
CHTUNGTRENNUNG
A
E
OCH2CH2O), 4.29 (m, 8H; OCH2CH2O), 6.57 (d, J=1.7 Hz, 4H; H-2’’),
6.73 (dd, J=8.3, 1.7 Hz, 4H; H-6’’), 6.78 (d, J=8.3 Hz, 4H; H-5’’),
9540
www.chemeurj.org
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 9530 – 9542

Dibenzo[18]crown-6 Derivatives
FULL PAPER
6.94 ppm (s, 4H; H-3, H-3’, H-6, H-6’); 13C NMR (CD2Cl2, 75 MHz): d=
14.3 (CH3), 23.1, 26.48, 26.51, 29.6, 29.80, 29.83, 29.88, 29.93, 30.10, 30.14,
Acknowledgements
30.17, 30.20, 32.36, 32.37 (OCH
2ACHTUNGRTNEUN(GN CH2)10CH3), 67.7, 69.4 (OCH2CH2O),
Generous financial support by the Deutsche Forschungsgemeinschaft, the
Max-Planck-Gesellschaft (fellowship of the International Max Planck Re-
search School for Advanced Materials for M.K.), the Fonds der Chemi-
schen Industrie, the Bundesministerium fꢁr Forschung und Bildung, and
the Ministerium fꢁr Wissenschaft, Forschung und Kunst des Landes
Baden-Wꢁrttemberg is gratefully acknowledged. We would like to thank
Prof. Clemens Richert for providing the MALDI-TOF MS equipment
and Dipl.-Ing. (FH) Joachim Trick for providing the TGA equipment.
69.6 (OCH2A(CH2)10CH3), 113.6, 113.7 (C-5’, C-3, C-3’, C-6, C-6’), 116.8
CHTUNGTRENNUNG
(C-2’’), 122.3 (C-6’’), 133.8, 134.4 (C-4, C-4’, C-5, C-5’, C-1’’), 146.1 (C-1,
C-1’, C-2, C-2’), 148.4, 148.8 ppm (C-3’’, C-4’’); FTIR (ATR): v˜ =2919,
2850 (vs), 2051 (w), 1498 (s), 1467 (m), 1456 (m), 1242 (vs), 1195 (m),
1133 (m), 1066 (w), 960 (w), 860 (w), 793 (m), 721 (w), 608 cmꢀ1 (m); MS
(MALDI-TOF): m/z: calcd for [C140H232O14K+]: 2176.7; found: 2176.8;
elemental analysis calcd (%) for C141H232KNO14S (2236.5): C 75.72, H
10.46, N 0.63, S 1.42; found: C 75.24, H 10.25, N 0.63, S 1.42.
4,4’,5,5’-Tetrakis[3’’,4’’-bis(dodecyloxy)phenyl]dibenzo[18]crown-6 potas-
sium tetrafluoroborate complex (KBF4·1g): Colorless solid; 1H NMR
(CD2Cl2, 300 MHz): d=0.86–0.90 (m, 24H; CH3), 1.27–1.47 (m, 144H;
[1] a) X. Zhang, N. Zhao, S. Liang, X. Lu, X. Li, Q. Xie, X. Zhang, J.
Xu, Adv. Mater. 2008, 20, 2938–2946; b) J. F. Mano, Adv. Eng.
Mater. 2008, 10, 515–527; c) A. Richter, G. Paschew, S. Klatt, J.
Lienig, K.-F. Arndt, H.-J. P. Adler, Sensors 2008, 8, 561–581; d) H.-J.
Kim, Y.-B. Lim, M. Lee, J. Polym. Sci. Polym. Chem. Ed. 2008, 46,
1925–1935; e) B. G. Trewyn, S. Giri, I. I. Slowing, V. S.-Y. Lin,
Chem. Commun. 2007, 3236–3245; f) Y. Lu, J. Liu, Acc. Chem. Res.
2007, 40, 315–323; g) A. J. Wilson, Soft Matter 2007, 3, 409–425;
O
G
E
2ACHTUNGTRENN(NUG CH2)9CH3), 1.71–1.81
CHTUNGTRENNUNG
A
CHTUNGTRENNUNG
OCH2CH2O), 4.22 (m, 8H; OCH2CH2O), 6.57 (d, J=1.6 Hz, 4H; H-2’’),
6.72 (dd, J=8.3, 1.6 Hz, 4H; H-6’’), 6.77 (d, J=8.3 Hz, 4H; H-5’’),
6.91 ppm (s, 4H; H-3, H-3’, H-6, H-6’); 13C NMR (CD2Cl2, 75 MHz): d=
14.3 (CH3), 23.1, 26.48, 26.52, 29.6, 29.80, 29.83, 29.87, 29.93, 30.10, 30.14,
´
h) S. Rieth, C. Baddeley, J. D. Badjic, Soft Matter 2007, 3, 137–154;
i) M. Behl, A. Lendlein, Soft Matter 2007, 3, 58–67.
30.17, 30.20, 32.36, 32.38 (OCH
69.6 (OCH2A(CH2)10CH3), 70.1 (OCH2CH2O), 113.7 (C-5’’), 115.2 (C-3, C-
2ACHTUNGRTNEUN(GN CH2)10CH3), 68.7 (OCH2CH2O), 69.5,
[2] Reviews: a) K. Praefcke, A. Eckert, Mol. Cryst. Liq. Cryst. 2003,
396, 265–299; b) K. Praefcke, D. Singer in Handbook of Liquid
Crystals, Vol. 2B (Eds.: D. Demus, J. Goodby, G. W. Gray, H.-W.
Spiess, V. Vill), Wiley-VCH, Weinheim, 1998, pp. 945–967; c) K.
Praefcke, J. D. Holbrey, J. Inclusion Phenom. Mol. Recognit. Chem.
1996, 24, 19–41; d) K. Praefcke, D. Singer, Mol. Cryst. Liq. Cryst.
Sci. Technol. Sect. C 1994, 3, 265–270.
CHTUNGTRENNUNG
3’, C-6, C-6’), 116.8 (C-2’’), 122.3 (C-6’’), 133.3, 134.8 (C-4, C-4’, C-5, C-5’,
C-1’’), 147.8 (C-1, C-1’, C-2, C-2’), 148.2, 148.8 ppm (C-3’’, C-4’’); FTIR
(ATR): v˜ =2954 (w), 2915 (vs), 2873 (w), 2849 (vs), 1504 (s), 1468 (m),
1450 (m), 1250 (vs), 1193 (m), 1136 (m), 1122 (m), 1069 (w), 804 (w), 800
(w), 612 cmꢀ1 (m); MS (MALDI-TOF): m/z: calcd for [C140H232O14K+]:
2176.7; found: 2176.3.
[3] Reviews: a) S. Pieraccini, A. Ferrarini, G. P. Spada, Chirality 2008,
20, 749–759; b) G. Gottarelli, G. P. Spada, Top. Stereochem. 2003,
24, 425–455; c) H.-D. Dçrfler, Adv. Colloid Interface Sci. 2002, 98,
285–340; d) H.-M. P. Chen, S. W. Culligan, Y. H. Geng, D. Katsis,
S. H. Chen, Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem. 2002,
43, 145–146; e) H.-G. Kuball, E. Dorr, EMIS Datarev. Ser. 2000, 25,
333–343; f) G. Gottarelli, G. P. Spada, G. Solladie, Nouv. J. Chim.
1986, 10, 691–696; g) G. P. Spada, G. Proni, Enantiomer 1998, 3,
301–314.
[4] Reviews: a) R. P. Lemieux, Chem. Soc. Rev. 2007, 36, 2033–2045;
b) C. S. Hartley, N. Kapernaum, J. C. Roberts, F. Giesselmann, R. P.
Lemieux, J. Mater. Chem. 2006, 16, 2329–2337; c) R. P. Lemieux,
Acc. Chem. Res. 2001, 34, 845–853; d) S. T. Lagerwall, Ferroelectric
and Antiferroelectric Liquid Crystals, Wiley-VCH, Weinheim, 1999;
e) J. W. Goodby, R. Blinc, N. A. Clark, S. T. Lagerwall, M. A.
Osipov, S. A. Pikin, T. Sakurai, K. Yoshino, B. Zeks, Ferroelectric
Liquid Crystals: Principles, Properties and Applications, Gordon and
Breech, Philadelphia 1991.
[5] a) R. P. Tuffin, G. H. Mehl, K. J. Toyne, J. W. Goodby, Mol. Cryst.
Liq. Cryst. 1997, 304, 223–230; b) R. P. Tuffin, K. J. Toyne, J. W.
Goodby, J. Mater. Chem. 1996, 6, 1271–1282; c) R. P. Tuffin, K. J.
Toyne, J. W. Goodby, J. Mater. Chem. 1995, 5, 2093–2104; d) A. J.
Blake, D. W. Bruce, J. P. Danks, I. A. Fallis, D. Guillon, S. A. Ross,
H. Richtzenhain, M. Schrçder, J. Mater. Chem. 2001, 11, 1011–1018;
e) J. A. Schrçter, C. Tschierske, M. Wittenberg, J. H. Wendorff,
Angew. Chem. 1997, 109, 1160–1163; Angew. Chem. Int. Ed. Engl.
1997, 36, 1119–1121.
[6] a) V. Percec, D. Schlueter, G. Ungar, S. Z. D. Cheng, A. Zhang,
Macromolecules 1998, 31, 1745–1762; b) V. Percec, G. Johansson, G.
Ungar, J. Zhou, J. Am. Chem. Soc. 1996, 118, 9855–9866; c) V.
Percec, D. Tomazos, J. Heck, H. Blackwell, G. Ungar, J. Chem. Soc.
Perkin Trans. 2 1994, 31–44; d) G. Johansson, V. Percec, G. Ungar,
D. Abramic, J. Chem. Soc. Perkin Trans. 1 1994, 447–459; e) V.
Percec, G. Johansson, J. Heck, G. Ungar, S. V. Batty, J. Chem. Soc.
Perkin Trans. 1 1993, 1411–1420; f) V. Percec, G. Johansson, R. Ro-
denhouse, Macromolecules 1992, 25, 2563–2565.
4,4’,5,5’-Tetrakis[3’’,4’’-bis(dodecyloxy)phenyl]dibenzo[18]crown-6 potas-
sium hexafluorophosphate complex (KPF6·1g): Pale brown solid;
1H NMR (CD2Cl2, 300 MHz): d=0.86–0.90 (m, 24H; CH3), 1.27–1.49 (m,
144H; O
1.71–1.81 (m, 8H; OCH2CH
(CH2)10CH3), 3.92 (t, J=6.6 Hz, 8H; OCH CHUTNGTRENNUNG
(CH2)
R
2ACHTUNGRTNE(NUNG CH2)9CH3),
CTHUNGTRENNUNG
U
OCH2CH2O), 4.27 (m, 8H; OCH2CH2O), 6.56 (d, J=1.7 Hz, 4H; H-2’’),
6.73 (dd, J=8.3, 1.7 Hz, 4H; H-6’’), 6.78 (d, J=8.3 Hz, 4H; H-5’’),
6.94 ppm (s, 4H; H-3, H-3’, H-6, H-6’); 13C NMR (CD2Cl2, 75 MHz): d=
14.3 (CH3), 23.1, 26.48, 26.51, 29.6, 29.81, 29.83, 29.88, 29.93, 30.10, 30.14,
30.17, 30.21, 32.4 (OCH
(OCH2A(CH2)10CH3), 113.7 (C-5’, C-3, C-3’, C-6, C-6’), 116.8 (C-2’’), 122.3
2CATHUNGTREN(NUNG CH2)10CH3), 67.7, 69.1 (OCH2CH2O), 69.6
CHTUNGTRENNUNG
(C-6’’), 133.8, 134.4 (C-4, C-4’, C-5, C-5’, C-1’’), 146.1 (C-1, C-1’, C-2, C-
2’), 148.5, 148.8 ppm (C-3’’, C-4’’); FTIR (ATR): v˜ =2921, 2852 (vs), 1496
(s), 1466 (m), 1457 (m), 1244 (vs), 1195 (m), 1124 (m), 1052 (w), 961 (w),
840 (vs), 793 (w), 612 (m), 558 cmꢀ1 (s); MS (MALDI-TOF): m/z: calcd
for [C140H232O14K+]: 2176.7; found: 2174.8; elemental analysis calcd (%)
for C140H232F6KO14P (2323.4): C 72.37, H 10.06, P 1.41; found: C 72.29, H
9.97, P 1.31.
4,4’,5,5’-Tetrakis[3’’,4’’-bis(dodecyloxy)phenyl]dibenzo[18]crown-6 ammo-
nium hexafluorophosphate complex (NH4PF6·1g): Pale brown solid;
1H NMR (CD2Cl2, 300 MHz): d=0.86–0.90 (m, 24H; CH3), 1.27–1.49 (m,
144H; O
1.72–1.81 (m, 8H; OCH2CH
(CH2)10CH3), 3.92 (t, J=6.6 Hz, 8H; OCH CHUTNGTRENNUNG
(CH2)
R
2ACHTUNGRTNE(NUNG CH2)9CH3),
CTHUNGTRENNUNG
U
OCH2CH2O), 4.31 (m, 8H; OCH2CH2O), 6.56 (d, J=1.7 Hz, 4H; H-2’’),
6.73 (dd, J=8.3, 1.7 Hz, 4H; H-6’’), 6.78 (d, J=8.3 Hz, 4H; H-5’’),
6.95 ppm (s, 4H; H-3, H-3’, H-6, H-6’); 13C NMR (CD2Cl2, 75 MHz): d=
14.3 (CH3), 23.1, 26.48, 26.51, 29.6, 29.81, 29.84, 29.89, 29.93, 30.10, 30.14,
30.18, 30.21, 32.4 (OCH
2CATHUNGTREN(NUNG CH2)10CH3), 67.5, 69.5 (OCH2CH2O), 69.6
(OCH2A(CH2)10CH3), 113.7, 114.0 (C-5’, C-3, C-3’, C-6, C-6’), 116.7 (C-2’’),
CHTUNGTRENNUNG
122.3 (C-6’’), 134.0, 134.3 (C-4, C-4’, C-5, C-5’, C-1’’), 145.8 (C-1, C-1’, C-
2, C-2’), 148.5, 148.8 ppm (C-3’’, C-4’’); FTIR (ATR): v˜ =3226 (w), 2920,
2852 (vs), 1497 (s), 1456 (m), 1243 (vs), 1195 (m), 1125 (m), 1066 (m),
959 (w), 839 (vs), 613 (m), 558 cmꢀ1 (s); MS (MALDI-TOF): m/z: calcd
for [C140H232O14+]: 2137.7; found: 2137.2; elemental analysis calcd (%)
for C140H232F6NO14P (2302.3): C 73.03, H 10.33, N 0.61, P 1.35; found: C
73.05, H 10.29, N 0.58, P 1.48.
[7] a) S. Laschat, A. Baro, N. Steinke, F. Giesselmann, C. Hꢀgele, G.
Scalia, R. Judele, E. Kapatsina, S. Sauer, A. Schreivogel, M. Tosoni,
Angew. Chem. 2007, 119, 4916–4973; Angew. Chem. Int. Ed. 2007,
46, 4832–4887; b) S. Sergeyev, W. Pisula, Y. H. Geerts, Chem. Soc.
Chem. Eur. J. 2009, 15, 9530 – 9542
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
9541

S. Laschat et al.
Rev. 2007, 36, 1902–1929; c) M. Peterca, V. Percec, A. E. Dulcey, S.
Nummelin, S. Korey, M. Ilies, P. A. Heiney, J. Am. Chem. Soc. 2006,
128, 6713–6720; d) T. Kato, N. Mizoshita, K. Kishimoto, Angew.
Chem. 2006, 118, 44–74; Angew. Chem. Int. Ed. 2006, 45, 38–68;
e) C. Tschierske, Annu. Rep. Prog. Chem. 2001, 97, 191–267; f) C.
Tschierske, J. Mater. Chem. 1998, 8, 1485–1508; g) J. W. Goodby,
G. H. Mehl, I. M. Saez, R. P. Tuffin, G. Mackenzie, R. Auzꢇly-Velty,
T. Benvegnu, D. Plusquellec, Chem. Commun. 1998, 2057–2070.
[8] a) U. Beginn, G. Zipp, M. Mçller, Adv. Mater. 2000, 12, 510–513;
b) U. Beginn, G. Zipp, A. Mourran, P. Walther, M. Mçller, Adv.
Mater. 2000, 12, 513–516; c) U. Beginn, G. Zipp, M. Mçller, Chem.
Eur. J. 2000, 6, 2016–2023.
[20] Reviews: a) C. J. Pedersen, J.-M. Lehn, D. J. Cram, Resonance 2001,
6, 71–79; b) J.-M. Lehn, Angew. Chem. 1988, 100, 91–116; Angew.
Chem. Int. Ed. Engl. 1988, 27, 89–112; c) D. J. Cram, Angew. Chem.
1988, 100, 1041–1052; Angew. Chem. Int. Ed. Engl. 1988, 27, 1009–
1020; d) C. J. Pedersen, Angew. Chem. 1988, 100, 1053–1059;
Angew. Chem. Int. Ed. Engl. 1988, 27, 1021–1027.
[21] a) M. d’Amboise, D. Noel, Anal. Chim. Acta 1985, 170, 255–264;
b) H. Sato, Y. Kusumoto, Chem. Lett. 1978, 635–638.
[22] D. Live, S. I. Chan, J. Am. Chem. Soc. 1976, 98, 3769–3778.
[23] J. C. Lockhart, A. C. Robson, M. E. Thompson, P. D. Tyson, I. H. M.
Wallace, J. Chem. Soc. Dalton Trans. 1978, 611–617.
[24] T. Sugawara, M. Yudasaka, Y. Yokoyama, T. Fujiyama, H. Iwamura,
J. Phys. Chem. 1982, 86, 2705–2709.
[25] M.-C. Fedarko, J. Magn. Reson. 1973, 12, 30–35.
[26] a) J. D. Dunitz, M. Dobler, P. Seiler, R. P. Phizackerley, Acta Crystal-
logr. Sect. B 1974, 30, 2733–2738; b) P. Seiler, M. Dobler, J. D.
Dunitz, Acta Crystallogr. Sect. B 1974, 30, 2744–2745.
[9] Y. Chen, W. Su, M. Bai, J. Jiang, X. Li, Y. Liu, L. Wang, S. Wang, J.
Am. Chem. Soc. 2005, 127, 15700–15701.
[10] a) C. F. van Nostrum, Adv. Mater. 1996, 8, 1027–1030; b) C. F. van
Nostrum, R. J. M. Nolte, Chem. Commun. 1996, 2385–2392; c) C. F.
van Nostrum, S. J. Picken, A.-J. Schouten, R. J. M. Nolte, J. Am.
Chem. Soc. 1995, 117, 9957–9965; d) C. F. van Nostrum, S. J. Picken,
R. J. M. Nolte, Angew. Chem. 1994, 106, 2298–2300; Angew. Chem.
Int. Ed. Engl. 1994, 33, 2173–2175; e) O. E. Sielcken, M. M. van Til-
borg, M. F. M. Roks, R. Hendriks, W. Drenth, R. J. M. Nolte, J. Am.
Chem. Soc. 1987, 109, 4261–4265; f) C. Sirlin, L. Bosio, J. Simon, V.
Ahsen, E. Yilmazer, ꢈ. Bekaroglu, Chem. Phys. Lett. 1987, 139,
362–364.
[11] a) M. Gutiꢇrrez-Nava, M. Jaeggy, H. Nierengarten, P. Masson, D.
Guillon, A. Van Dorsselaer, J.-F. Nierengarten, Tetrahedron Lett.
2003, 44, 3039–3042; b) P. Samorꢉ, H. Engelkamp, P. de Witte, A. E.
Rowan, R. J. M. Nolte, J. P. Rabe, Angew. Chem. 2001, 113, 2410–
2412; Angew. Chem. Int. Ed. 2001, 40, 2348–2350; c) H. Engelkamp,
S. Middelbeek, R. J. M. Nolte, Science 1999, 284, 785–788.
[12] a) D. J. Abdallah, R. G. Weiss, Adv. Mater. 2000, 12, 1237–1247;
b) K. Murata, M. Aoki, T. Nishi, A. Ikeda, S. Shinkai, J. Chem. Soc.
Chem. Commun. 1991, 1715–1718.
ˇ ´
ˇ
ˇ ´
[27] P. Dapporto, P. Paoli, I. Matijasic, L. Tusek-Bozic, Inorg. Chim. Acta
1996, 252, 383–389.
[28] A. Bianchi, J. Giusti, P. Paoletti, S. Mangani, Inorg. Chim. Acta
1986, 117, 157–164.
[29] a) J. M. Harrington, S. B. Jones, P. H. White, R. D. Hancock, Inorg.
Chem. 2004, 43, 4456–4463; b) J. Dou, X. Gao, F. Dong, D. Li, D.
Wang, Dalton Trans. 2004, 2918–2922; c) D.-C. Li, Z.-X. Li, J.-M.
Dou, D.-Q. Wang, J. Inclusion Phenom. Macrocyclic Chem. 2003, 46,
83–88; d) H. Zhang, X. Wang, B. K. Teo, J. Am. Chem. Soc. 1996,
118, 11813–11821.
[30] L. C. Manege, T. Takayanagi, M. Oshima, S. Motomizu, Analyst
2000, 125, 699–703.
[31] S. Krishna Prasad, D. S. S. Rao, S. Chandrasekhar, S. Kumar, Mol.
Cryst. Liq. Cryst. 2003, 396, 121–139.
[32] A. M. Levelut, J. Chim. Phys. Phys.-Chim. Biol. 1983, 80, 149–161.
[33] N. F. M. Henry, K. Lonsdale, International Tables for X-Ray Crystal-
lography, Kynoch Press, Birmingham, 1965.
[13] N. Steinke, W. Frey, A. Baro, S. Laschat, C. Drees, M. Nimtz, C.
Hꢀgele, F. Giesselmann, Chem. Eur. J. 2006, 12, 1026–1035.
[14] N. Steinke, M. Jahr, M. Lehmann, A. Baro, W. Frey, S. Tussetschlꢀ-
ger, S. Sauer, S. Laschat, J. Mater. Chem. 2009, 19, 645–654.
[15] A. Schultz, S. Laschat, A. Saipa, F. Giesselmann, M. Nimtz, J. L.
Schulte, A. Baro, B. Miehlich, Adv. Funct. Mater. 2004, 14, 163–168.
[16] S. Mochizuki, A. Wakisaka, J. Phys. Chem. A 2002, 106, 5095–5100.
[17] U. Olsher, J. Am. Chem. Soc. 1982, 104, 4006–4007.
[34] M. Lehmann, C. Kçhn, H. Meier, S. Renker, A. Oehlhof, J. Mater.
Chem. 2006, 16, 441–451.
[35] ChemBio3D Ultra 11.0, Cambridge Soft, 2007.
[36] H. Zheng, C. K. Lai, T. M. Swager, Chem. Mater. 1995, 7, 2067–
2077.
[37] C. K. Lai, C.-H. Tsai, Y.-S. Pang, J. Mater. Chem. 1998, 8, 1355–
1360.
[38] a) XACQ 4.0.4; b) XMASS/XTOF 5.1.0, Bruker Daltonics.
[39] SAXS 4.1.26, Bruker AXS, 2001.
[18] a) M. J. Sienkowska, J. M. Farrar, F. Zhang, S. Kusuma, P. A.
Heiney, P. Kaszynski, J. Mater. Chem. 2007, 17, 1399–1411; b) A. R.
Surrey, L. I. Smith, C.-P. Lo, Org. Synth. 1946, 26, 90.
[40] A. Schultz, Dissertation, Technische Universitꢀt Braunschweig (Ger-
many), 2003.
[19] N. D. Lowe, C. D. Garner, J. Chem. Soc. Dalton Trans. 1993, 2197–
2207.
Received: May 4, 2009
Published online: August 5, 2009
9542
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ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 9530 – 9542