Ladder type supramolecular assembly and gas adsorption profile under reduced pressure based on hydrogen bonded m-tetraphenyl derivative of anthracene

Article abstract of DOI:10.1016/j.tet.2007.04.046

We report a guest adduct X-ray structures and gas adsorption capability of 9,10-bis(4″,4-dihydroxyl-m-terphen-5″-yl)anthracene, which is an analogue of anthracene-bis(resorcinol) derivative reported by Aoyama et?al. The gas adsorption capability is double

Full text of DOI:10.1016/j.tet.2007.04.046

Tetrahedron 63 (2007) 6887–6894
Ladder type supramolecular assembly and gas adsorption
profile under reduced pressure based on hydrogen bonded
m-tetraphenyl derivative of anthracene
Kazuhiko Akimoto,a Hideo Suzuki,b Yoshihiko Kondo,c Ken Endo,c Uichi Akiba,c
Yasuhiro Aoyamad and Fumio Hamadac,
*
aElectronic Materials Research Laboratories, Nissan Chemical Industries, Ltd, 635 Sasakura, Fuchu-Machi, Toyama 939-2792, Japan
bCentral Research Institute, Nissan Chemical Industries, Ltd, 722 Tsuboi-cho, Funabashi, Chiba 274-8507, Japan
cDepartment of Materials-Process Engineering and Applied Chemistry for Environments, Akita University,
1-1 Tegatagakuen-cho, Akita 010-8502, Japan
dDepartment of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University,
Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
Received 15 February 2007; revised 14 April 2007; accepted 16 April 2007
Available online 20 April 2007
Abstract—We report a guest adduct X-ray structures and gas adsorption capability of 9,10-bis(400,4-dihydroxyl-m-terphen-500-yl)anthracene,
which is an analogue of anthracene-bis(resorcinol) derivative reported by Aoyama et al. The gas adsorption capability is double scale of guest
inclusion than that of anthracene-bis(resorcinol) derivative.
Ó 2007 Elsevier Ltd. All rights reserved.
1. Introduction
supramolecular architecture was used as molecular reaction
flask, the flask should have enough size to incorporate two
guest molecules. It would be favorable if a large cavity was
constructed by molecular design. Here we present a new
bis(resorcinol) derivative of anthracene as a ladder type
supramolecular architecture (1), in which benzene unit was
introduced as a spacer to enlarge a guest incorporated
domain. In this study, we succeeded to make a couple of
crystal structures, which are 1$3(CH3COC2H5)$2(p-xylene),
1$3(CH3COOC2H5)$2(p-xylene), 1$5(CH3COOC2H5), and
1$4(CH3COCH3). Also we investigated the gas adsorption
profile of 1 with a couple of guest molecules, such as
MEK, acetone, EtOAc, and benzene. It was found that gas
adsorption capability of 1 shows two times of guest molecules
compared with that of 2, in which two molecules were in-
cluded in the cavity and another two molecules were trapped
between the sheets of ladder like structure. In the system,
interactions involving hydroxyl groups have been shown to
play an important role in the formation organization.
Hydrogen bonding interactions as well as electrostatic
forces, van der Waals, and p–p stacking interactions, are
the main force for the self-assembly of supramolecular for-
mation, which have recently received much attention be-
cause of their versatile functionality such as guest binding
with vacancies of defined size and shape to entrap the guest
molecule.1
Fifteen years ago, a synthesis of bis(resorcinol) derivative of
anthracene (2), which forms a hydrogen bonded 2D network,
has been reported by Aoyama et al. The resulting huge cav-
ities are capable of binding guest molecules.2 After that,
a couple of analogues of resorcinol derivative of anthracene
such as stacked porphyrin arrays by hydrogen bonded net-
work,3 a robust two-dimensional hydrogen bonded network4
based on anthracene monoresorcinol, have been synthesized
in order to evaluate the capability of gas adsorption property,
because design of crystal structures is still a tough challenge
in materials science and technology.5 However, these
analogues have some problems, which have too small cavity
size to entrap two different guest molecules. When de novo
2. Results and discussion
2.1. The preparation of tetraphenylhydroxyl derivative
of anthracene (1)
Keywords:Anthracene;Coordinationbond;Silvertrifluoromethanesulfonate;
Adsorption isotherms.
The synthesis of 1 was achieved by three steps in high yields
as shown in Scheme 1. The starting material 2 was
* Corresponding author. Tel.: +81 18 889 2440; fax: +81 18 837 0404;
e-mail: hamada@ipc.akita-u.ac.jp
0040–4020/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2007.04.046

6888
K. Akimoto et al. / Tetrahedron 63 (2007) 6887–6894
TfO
OTf
HO
HO
OH
OH
4-Methoxyphenylbromic acid
Pd(PPh)3, LiCl
Tf2O
2,6-lutidine
TfO
OTf
2
3
HO
OH
MeO
OMe
BBr3
HO
OH
MeO
4
1
OMe
Scheme 1. Preparation of 1.
synthesized by Aoyama et al. Later, a couple of derivatives
of it were prepared to investigate functionalities such as
gas sorption and self-assembly formation. Introduction of
benzene unit to 2 was succeeded in Suzuki cross coupling
reaction in high yield.6
2.2. Crystal structures of 1 with several guest molecules
Table 1. Crystallization from various conditions
The crystals suitable for X-ray study were obtained by
liquid–liquid slow diffusion of a poor solvent into a good
solvent of 1 at room temperature as shown in Table 1. In
cases of entries 1, 2, 4, and 7 in Table 1, the single crystals
were obtained as to be suitable for X-ray analysis. In the
other entries 3, 5, 6, and 8, adduct of guest molecular ratios
Entry Guest A
(good solvent)
Guest B
(poor solvent)
Guest A/host Guest B/host
1a
2a
3
MEK
AcOEt
AcOEt
AcOEt
Acetone
Acetone
Acetone
Methyl benzoate
p-Xylene
p-Xylene
Benzene
—
p-Xylene
Benzene
—
3
2
3
2
—
5
2
2
—
2
4a
5
1
were detected with integration of H NMR, because those
6
—
4
1
2
—
—
crystals were too small for X-ray analysis. Crystal data and
parameters of refinement for 1$3(CH3COC2H5)$2(p-xylene),
1$3(CH3COOC2H5)$2(p-xylene), 1$5(CH3COOC2H5), and
1$4(CH3COCH3) are summarized in Table 2.
7a
8
—
a
The single crystals were obtained as to be suitable for X-ray analysis.
Table 2. Crystal data of 1 with various guest molecules
Adduct
p-Xylene MEK
p-Xylene AcOEt
AcOEt
Acetone
Formula
C78H78O7
1127.47
Triclinic
P-1
C82H86O12
1263.57
Triclinic
P-1
C74H82O16
1227.45
Triclinic
P-1
C62H58O8
931.14
Monoclinic
P-1 21/n1
Yellow
0.500ꢀ0.300ꢀ0.250
14.3194(4)
9.0878(3)
19.4726(6)
90
97.563(1)
90
2512.0(1)
2
1.231
163.2
0.08
20,821
5666
374
0.055
1.857
0.2841
Formula weight
Crystal system
Space group
Color
Yellow
Yellow
Yellow
Size (mm)
˚
0.600ꢀ0.450ꢀ0.400
11.7930(5)
11.8241(5)
13.8497(7)
75.565(2)
68.929(3)
61.372(1)
1574.8(1)
1
1.189
163.2
0.074
14,772
0.800ꢀ0.600ꢀ0.600
11.7863(3)
12.1310(4)
13.864(1)
87.451(2)
66.360(3)
62.936(4)
1593.7(2)
1
1.316
163.2
0.087
13,945
0.500ꢀ0.500ꢀ0.500
11.8068(1)
11.8656(3)
14.0903(3)
88.846(2)
67.9064(1)
64.164(5)
1621.57(9)
1
1.257
163.2
0.088
10,537
a (A)
˚
b (A)
˚
c (A)
a (deg)
b (deg)
g (deg)
3
˚
V (A )
Z
Dcalc (g/cm3)
T (K)
m¼(Mo Ka) (cmꢁ1
)
No. of reflections measured
No. of reflections used
No. of variables
R1
GOF
wR2
7109
457
0.033
1.827
0.2286
7107
489
0.047
1.709
0.2127
6447
433
0.105
1.916
0.3559

K. Akimoto et al. / Tetrahedron 63 (2007) 6887–6894
6889
Figure 1a shows the crystal structure of 1$3MEK$2p-xylene.
The two p-xylene of the guest molecules were located at the
parallel and the two MEK of M1 and M3 could not be repre-
sented precisely because these molecules were disordered. It
was shown that the crystal of adduct of 1$3MEK$2p-xylene
constructed ladder like network, which was hydrogen
bonded network such as ladder like framework as shown in
Scheme 2a and b. Appended moiety linked with anthracene
overlapped each other and resulted to make molecular sheet
along c axis. It was known that two kinds of cavities are pres-
ent in this structure, which was made from ladder structure
and the other from molecular sheet, respectively, as shown
in Figure 2a and b. The big cavity was made from ladder
structure in parallel with the bc plane, of which the longitu-
˚
bonded with a O/O distance of 2.796 A, as shown in
Figure 1b. Although, it has been reported that supramole-
cular assembly based on anthracene derivative such as 21
formed hydrogen bonded network in a cancellous structure
depicted, it was recognized that 1 formed different hydrogen
˚
dinal and lateral direction sizes are 13.850 and 15.473 A,
(a)
(b)
Scheme 2. (a) Model of cancellous structure and (b) ladder like structure.
Figure 1. (a) Crystal structure of 1$3MEK$2p-xylene. The carbons,
oxygens, and hydrogens in the host molecules are gray, red, and white,
respectively. The p-xylene and MEK of the guest molecules are green and
pink. (b) Location of host and guest molecules along a axis.
Figure 2. (a) Sheet structure along c axis. (b) Ladder structure of molecular
sheet in parallel with the bc plane.

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K. Akimoto et al. / Tetrahedron 63 (2007) 6887–6894
small one includes two p-xylenes and one MEK. As shown
in Figure 3, it was observed as the very interesting location
of the guest molecule inclusion in the large cavity, in which
there included one MEK that was connected with hydroxyl-
phenyl group of 1 by the hydrogen bonding and CH–p inter-
action with anthracene parts of 1 with a O/O distances of
˚
˚
ca. 2.723 A and 3.589–3.831 A, respectively. In addition, it
was also found that the CH–p interaction between MEK
and p-xylene, which were located in the small cavity, with
˚
a distance of ca. 3.847 A. Another two MEK molecules
located in outside of these cavities. It was indicated that
the stability of MEK included in the small cavity was not
so strong, because this guest molecule has no interaction
with surrounding species. It was shown that the conforma-
tions of crystal structures of 1$3ethylacetate$2p-xylene
and 1$5ethylacetate were very similar to complex of
1$3MEK$2p-xylene. Figure 4 shows the structure of the ad-
duct of 1$3ethylacetate$2p-xylene, in which one hydrogen
bonded ethylacetate was included in the large cavity. The
other four guest molecules (two ethylacetate and p-xylene)
were included in the layer made from the molecular sheet
along the [110] direction. It was shown that the O/O
distance between ethylacetate and hydroxylphenyl of 1 is
Figure 3. Location of host and guest molecules in the crystal. The p-xylene
and MEK of the guest molecules are green and pink.
˚
2.681 A. Figure 5 shows the structure of adduct of 1$5ethyl-
respectively. On the other hand, the smaller cavity originated
˚
from molecular sheet, of which the distance is 10.356 A. It
was shown that the large cavity included two MEK, and
acetate, in which two of the hydrogen bonded ethylacetate
molecules were included in the large cavity and other three
guest molecules in the layer made of molecular sheet along
direction [110]. The O/O distance between ethylacetate
Figure 4. Crystal structure of adduct of 1$3ethylacetate$2p-xylene along
b axis. The carbons, oxygens, and hydrogens in the host molecules are
gray, red, and white, respectively. The p-xylene and ethylacetate of the guest
molecules are green and pink.
Figure 5. Crystal structure of adduct of 1$5ethylacetate along b axis. The
carbons, oxygens, and hydrogens in the host molecules are gray, red, and
white, respectively. The ethylacetate of the guest molecule is blue.

K. Akimoto et al. / Tetrahedron 63 (2007) 6887–6894
6891
Figure 6. Structure of molecular sheet in parallel along direction [10ꢁ1].
10 m2/g obtained by an adsorption isotherm of N2 at 77 K.
In spite of this condensed nature, an apohost which is capa-
ble of crystalline phase guest addition and removal would be
noteworthy. Binding isotherms for gaseous guests with apo-
host is shown in Figure 8, where molar ratio of guest bound
to the apohost used is plotted against guest pressure at 25 ꢂC
for the adsorption. On adsorption of ethylacetate within the
saturation vapor pressure (Ps¼114 Torr), at the beginning,
ca. two molecules per host are absorbed into the apohost,
˚
and hydroxylphenyl of 1 is 2.683 A. Although the crystal
structure of adduct of 1$4 acetone was formed as a ladder
like structure of host assembly, the conformation is different
from those of adducts of 1$3MEK$2p-xylene, 1$3ethyl-
acetate$2p-xylene, and 1$5ethylacetate. It was recognized
that the molecular sheet from adduct of 1$4 acetone formed
zigzag structure along direction [10ꢁ1] in the crystal as
shown in Figure 6. It was shown that the crystal has a very
complicated structure, in which four host molecules made
the large cavity and one host molecule was included in a
different direction from those four host molecules in this re-
sulted cavity as indicated in Figure 7. As a result, a planate
sheet structure was formed as a layer, which included four
acetone molecules. In this crystal, each host molecule inter-
acted with neighboring host molecule by hydrogen bonding
˚
with a O/O distance of 2.653 A, which made sheet struc-
ture with a same direction. In those guest molecules, two
acetone molecules were bonded with hydroxylphenyl moi-
ety of 1 by hydrogen bonding with a O/O distance of
˚
2.732 A. The reason for the formation of the zigzag structure
of the complex 1$4 acetone might be explained by packing
of large cavity by neighboring host molecule. It was
estimated that it was not enough to fill up such a large cavity
with the guest molecules such as p-xylene and MEK,
because acetone was smaller than those of such guest
molecules.
2.3. Guest binding to apohost of 1
Heating at 100 ꢂC in vacuo an adduct of 1$3MEK$2p-xylene
resulted in a complete loss of guest molecules. The resulting
apohost 1 is non-crystalline as judged by its powder X-ray
diffraction pattern, and small specific surface ABET is below
Figure 7. Location of among host and guest molecules. Included a host
molecule in a different direction is blue. Acetone outside the large cavity
is green. Acetone inside the large cavity is pink.

6892
K. Akimoto et al. / Tetrahedron 63 (2007) 6887–6894
used as a guest, two and half acetone molecules’ adsorption
5
was seen. It might be due to small molecular size of acetone.
When vapor pressure was reduced, there remained two
guest molecules. It was suggested that remaining two
molecules are bounded by hydrogen bonding. On the other
hand, non-polar guest molecules such as n-hexane and
benzene were also studied. It was recognized that benzene
was adsorbed in a ratio of two molecules as shown in
Figure 9. It might be caused by the affinity between aromatic
rings.
4.5
4
3.5
3
2.5
2
3. Conclusion
In this study, it was shown that 9,10-bis(400,4-dihydroxyl-m-
terphen-500-yl)anthracene (1) can get ladder like hydrogen
bonding network in the presence of guest molecules, which
has a column structure.
1.5
1
0.5
0
It was shown that there are two kinds of cavities, which
contains ladder framework and sheet framework. It was
observed that four or five guest molecules were adsorbed
in the system, which is twice as high as that of anthracene-
bis(resorcinol) derivatives. It was confirmed that two
molecules, which bonded with 1 by hydrogen bonding,
were included in the ladder framework, and the other two
or three molecules were included in the space obtained
from the sheet framework. It is undergoing to study catalysis
by the apohost, because the host can entrap both polar and
non-polar substances, which might accelerate a reaction.
0
0.2
0.4
Pe / Ps
0.6
0.8
1
Figure 8. Binding isotherms for non-polar guest molecules of acetone (ꢃ),
ethylacetate (B), and MEK (:) adsorption at 25 ꢂC with apohost as 1.
in which hydrogen bonded network might be formed. And
then, more adsorption of guests was recognized, in which
the guest molecules might be included in the sheet structure.
Not only ethylacetate but also other guests such as acetone,
MEK can also be bound under similar condition. It was
observed that two molecules were adsorbed first and
then removal of guests was observed. On the other hand,
a different phenomenon was observed in the case of acetone
4. Experimental
4.1. General
9,10-Bis(3,5-dihydroxyl-1-phenyl)anthracene (2) was
synthesized as reported previously.2 1H NMR spectra were
obtained with Bruker DPX 300 spectrometer. IR spectra
were obtained with a Perkin–Elmer SPECTRUM 2000
spectrophotometer. X-ray powder diffractions were obtained
with Rigaku RAD-PC X-ray diffractometer (30 kV, 20 mA,
2.5
2
˚
Cu Ka radiation with l¼1.5418 A).
4.2. Synthesis
1.5
1
4.2.1. Preparation of triflate derivative of 9,10-bis(3,5-di-
hydroxyl-1-phenyl)anthracene (3). To a CH2Cl2 solution
containing 2 (3.24 g, 8.25 mol) cooled in an ice bath, 2,6-
lutidine (19.06 mL, 80.25 mmol) and trifluoromethane sul-
fonic anhydride (14.7 mL, 80.25 mmol) were added and
stirred for 6 h at room temperature. The reaction mixture
was concentrated in vacuo and the obtained residue was ex-
tracted with chloroform. The chloroform layer was washed
with water, saturated copper sulfate solution, water, and
saturated saline. The organic layer was dried over Na2SO4,
filtered, and evaporated to crude product, which was washed
with ethanol and filtered to give a triflate derivative 9,10-
bis(3,5-dihydroxyl-1-phenyl)anthracene (6.77 g, 89% yield).
0.5
0
0
0.2
0.4
0.6
0.8
1
Pe / Ps
1H NMR (300 MHz, DMSO-d6/CDCl3): d 8.260 (s, 2H,
phenyl-H), 7.825–7.833 (d, 4H, phenyl-H), 7.519 (m, 8H,
anthracene-H).
Figure 9. Binding isotherms for molar ratio of guest molecules of n-hexane
(ꢃ) and benzene (B) adsorption at 25 ꢂC with apohost as 1.

K. Akimoto et al. / Tetrahedron 63 (2007) 6887–6894
6893
4.2.2. Preparation of 9,10-bis(400,4-dimethoxyl-m-ter-
phen-500-yl)anthracene (4). To a solution containing 3
(2.00 g, 2.17 mmol), 4-methoxylphenyl boronic acid (1.46 g,
9.54 mmol), LiCl (2.21 g, 52.1 mmol), and Pd(PPh3)4 (1.01 g,
0.87 mmol) in a mixture of 25 mL of ethanol, 150 mL of
dioxane was added in the condition of light shielding. 2 M
Na2CO3 (4.25 g, 40.1 mmol) in aqueous solution (20 mL)
was added drop-wise to the reaction mixture. The reaction
mixture was stirred at 90 ꢂC for 24 h. Then, the reaction mix-
ture was concentrated to remove organic solvents and ex-
tracted with chloroform. The organic layer was washed with
dilutedhydrochloricacid, water, saturatedsodiumbicarbonate
water, water, and saturated saline, and then the organic layer
was dried over Na2SO4 and filtered. The mother liquid was
concentrated andtheobtainedresiduewas washed with ethanol,
filtered, and dried in vacuo to give pure 9,10-bis(400,4-di-
methoxyl-m-terphen-500-yl)anthracene (1.57 g, 95.7% yield).
solvent of 1 at room temperature. All measurements of
X-ray data were carried out on a Rigaku RAXIS-RAPID
imaging plate diffractometer.
4.3.1. Crystal data of 1$3MEK$2p-xylene. C78H78O7,
M¼1127.47, yellow, crystal dimensions 0.60ꢀ0.45ꢀ
0.40 mm, triclinic, space group P-1, a¼11.7930(5),
˚
b¼11.8241(5), c¼13.8497(7) A, a¼75.565(2), b¼68.929(3),
3
˚
g¼61.372(1) deg, V¼1574.8(1) A , Z¼1, Mo Ka radiation
rcalc¼1.189 g cmꢁ3, T¼163.2 K, numerical absorption cor-
rection, m(Mo Ka)¼0.074 cmꢁ1, data collections using
Rigaku RAXIS-RAPID imaging plate diffractometer, 14,772
measured reflections, 7116 unique reflections (Rint¼0.0847),
4991 observed reflections (I>3.00s(I)), 457 parameters,
R¼0.033, wR¼0.2286, refind against jFj, GOF¼1.827. All
crystallographic data of the crystals have been deposited at
the Cambridge Crystallographic Data Center in CIF format
CCDC no. 632059. Copies of the data can be obtained
free of charge on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (e-mail:deposit@ccdc.cam.ac.uk).
1H NMR (300 MHz, DMSO-d6/CDCl3):d 8.06(s, 2H, phenyl-
H), 7.77–7.83(m, 12H,phenyl-H), 7.63(q,4H, anthracene-H),
7.02–7.056 (d, 8H, phenyl-H), 3.80 (s, 12H, OCH3).
4.3.2. Crystal data of 1$3ethylacetate$2p-xylene.
C82H86O12, M¼1263.57, yellow, crystal dimensions
0.80ꢀ0.60ꢀ0.50 mm, triclinic, space group P-1, a¼
13C NMR (75 MHz, DMSO-d6/CDCl3): d 159.0 (s), 140.9
(s), 139.4 (s), 136.5 (s), 132.6 (s), 129.4 (s), 127.9 (s),
127.3 (s), 125.0 (s), 114.0 (s), 54.9 (s).
˚
11.7863(3), b¼12.1310(4), c¼13.864(1) A, a¼87.451(2),
3
˚
b¼66.360(3), g¼62.936(4) deg, V¼1593.7(2) A , Z¼1,
4.2.3. Preparation of 9,10-bis(400,4-dihydroxyl-m-ter-
phen-500-yl)anthracene (1). To a solution containing 3
(13.7 g, 18 mmol) in CH2Cl2 (125 mL) cooled in an ice
bath, boron tribromide (23.4 g, 93.4 mmol) in CH2Cl2
(250 mL) was added drop-wise in the condition of light
shielding. The reaction mixture was stirred for 12 h. Then,
the reaction mixture was cooled in an ice bath and treated
with 300 mL of water to quench excess of BBr3. After
CH2Cl2 was removed in vacuo, the aqueous layer was
extracted with EtOAc. The organic layer was washed with
saturated sodium bicarbonate water, water, and saturated
saline, and then the organic layer was dried over Na2SO4
and filtered. The organic layer was concentrated under re-
duced pressure to give oily residue. The residue was treated
with activated carbon, filtered, and then purified with silica
gel flush column chromatography. Elution with EtOAc
gave fractions containing corresponding product, which
was concentrated to remove solvent and resulting product
was treated with a mixture of EtOAc and chloroform to
give 1 (12.2 g, 96.1% yield) as precipitates.
Mo Ka radiation, rcalc¼1.316 g cmꢁ3, T¼163.2 K, numeri-
cal absorption correction, m(Mo Ka)¼0.087 cmꢁ1, data
collections using Rigaku RAXIS-RAPID imaging plate
diffractometer, 13,945 measured reflections, 7114 unique
reflections (Rint¼0.0896), 7107 observed reflections
(I>3.00s(I)), 489 parameters, R¼0.047, wR¼0.2127, refind
against jFj, GOF¼1.709. All crystallographic data of the
crystals have been deposited at the Cambridge Crystallo-
graphic Data Center in CIF format CCDC no. 632062.
Copies of the data can be obtained free of charge on applica-
tion to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
(e-mail:deposit@ccdc.cam.ac.uk).
4.3.3. Crystal data of 1$5ethylacetate. C74H82O16,
M¼1227.45, yellow, crystal dimensions 0.50ꢀ0.50ꢀ
0.50 mm, triclinic, space group P-1, a¼11.8068(1),
˚
b¼11.8656(3), c¼14.0903(3) A, a¼88.846(2), b¼
3
˚
67.9064(1), g¼64.164(5) deg, V¼1621.57(9) A , Z¼1, Mo
Ka radiation, rcalc¼1.257 g cmꢁ3, T¼163.2 K, numerical
absorption correction, m(Mo Ka)¼0.088 cmꢁ1, data collec-
tions using Rigaku RAXIS-RAPID imaging plate diffrac-
tometer, 10,537 measured reflections, 6453 unique
reflections (Rint¼0.1578), 6447 observed reflections (I>
3.00s(I)), 433 parameters, R¼0.105, wR¼0.3559, refind
against jFj, GOF¼1.916. All crystallographic data of the
crystals have been deposited at the Cambridge Crystallo-
graphic Data Center in CIF format CCDC no. 632060. Cop-
ies of the data can be obtained free of charge on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (e-mail:
deposit@ccdc.cam.ac.uk).
1H NMR (300 MHz, DMSO-d6): d 9.58 (s, 4H, phenyl-H),
7.98 (s, 2H, phenyl-H), 7.76–7.79 (m, 4H, anthracene-H),
7.67 (d, 8H, phenyl-H), 7.55 (d, 4H, phenyl-H), 6.88 (d,
8H, phenyl-H).
13C NMR (75 MHz, DMSO-d6/CDCl3): d 157.6 (s), 141.3
(s), 139.4 (s), 136.9 (s), 130.7 (s), 129.5 (s), 127.9 (s),
128.4 (s), 126.8 (s), 125.9 (s), 123.2 (s), 116.0 (s), 79.3 (s).
IR (KBr): 3342, 1610, 1598, 1513, 1229, 1175, 1106, 829,
787, 759 cmꢁ1
.
4.3.4. Crystal data of 1$4 acetone. C62H58O8, M¼931.14,
yellow, crystal dimensions 0.50ꢀ0.30ꢀ0.25 mm, mono-
4.3. Crystal data of 1 with solvents
clinic, space group P-1 21/n1, a¼14.3194(4), b¼9.0878(3),
3
˚
˚
c¼19.4726(6) A, b¼97.563(1) deg, V¼2512.0(1) A , Z¼2,
Mo Ka radiation, rcalc¼1.231 g cmꢁ3, T¼163.2 K, numeri-
cal absorption correction, m(Mo Ka)¼0.08 cmꢁ1, data
The crystals suitable for X-ray study were obatined by
liquid–liquid slow diffusion of a poor solvent into a good

6894
K. Akimoto et al. / Tetrahedron 63 (2007) 6887–6894
collections using Rigaku RAXIS-RAPID imaging plate
diffractometer, 20,821 measured reflections, 5666 unique
reflections (Rint¼0.1139), 374 observed reflections
(I>3.00s(I)), 374 parameters, R¼0.055, wR¼0.2841, refind
against jFj, GOF¼1.857. All crystallographic data of the
crystals have been deposited at the Cambridge Crystallo-
graphic Data Center in CIF format CCDC no. 632061.
Copies of the data can be obtained free of charge on applica-
tion to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
(e-mail:deposit@ccdc.cam.ac.uk).
become smaller than 1% of the pressure at the point. All
operations were computer-controlled and automatic. The
specific surface areas (ABET) were obtained by using the
same apparatus. The adsorption isotherm for N2 at 77 K
cannot fit well with BET equation, Pe/V(PeꢁPs)¼
1/VmC+[(Cꢁ1)/VmC](Pe/Ps), where Ps is saturation vapor
pressure of N2 at 77 K and is 760 Torr, V (mL/g) is the
amount (in terms of volume in the standard state) of N2
adsorbed per gram of adsorbent, Vm is saturation monolayer
coverage, and C is a constant.
4.4. Gas absorption measurements of 1
References and notes
The isotherm measurements for EtOAc, acetone, MEK,
benzene, and n-hexane were performed at 298 K by using
an automatic volumetric adsorption apparatus (BELSORP
18SP-V; BEL Inc.). In the sample chamber (ca. 15 mL)
maintained at 25.0ꢄ0.1 ꢂC was placed apohost as
1$3MEK$2p-xylene complex (ca. 200 mg), which has
been pretreated at 60 ꢂC at <10ꢁ3 Torr for 5 h just prior to
use. The larger gas chamber (176.36 mL) with a pressure
gauge was kept at 50ꢄ0.1 ꢂC. Helium gas at certain pressure
was introduced in the gas chamber and was allowed to
diffuse into the sample chamber by opening a valve. The
change in pressure allowed an accurate determination of
volume of the total gas phase. Host–guest complexation
was monitored in a similar manner by using a guest vapor
in place of He. The amount of guest adsorbed was calculated
readily from the pressure difference (PcalꢁPe), where Pcal is
the calculated pressure if there were no guest adsorption, as
in the case of helium, and Pe is the observed equilibrium
pressure, as which the change in pressure in 600 s had
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