A porous coordination architecture assembled by silver triflate and 9,10-bis(3,5-dicyano-1-phenyl)anthracene and its gas adsorption profile

Article abstract of DOI:10.1016/j.tetlet.2008.10.044

We report a crystal structure and guest uptake measurements of a 2D coordination polymer, 3·2(AgOTf)·2(acetone) which has been assembled by silver triflate and 9,10-bis(3,5-dicyano-1-phenyl)anthracene (3). When the as-prepared sample was evacuated, the 3·

Full text of DOI:10.1016/j.tetlet.2008.10.044

Tetrahedron Letters 49 (2008) 7361–7363
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Tetrahedron Letters
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A porous coordination architecture assembled by silver triflate and
9,10-bis(3,5-dicyano-1-phenyl)anthracene and its gas adsorption profile
Kazuhiko Akimoto a,b, Yoshihiko Kondo a, Ken Endo a, Manabu Yamada a, Yasuhiro Aoyama c,
Fumio Hamada a,
*
a Department of Materials-process Engineering and Applied Chemistry for Environments, Faculty of Engineering and Resource Science, Akita University, Akita 010-8502, Japan
b Electronic Materials Research Laboratories, Nissan Chemical Industries, Ltd, 635 Sasakura Fuchu-Machi, Toyama 939-2792, Japan
c Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
We report
a crystal structure and guest uptake measurements of a 2D coordination polymer,
Received 12 September 2008
Accepted 6 October 2008
Available online 14 October 2008
3ꢀ2(AgOTf)ꢀ2(acetone) which has been assembled by silver triflate and 9,10-bis(3,5-dicyano-1-
phenyl)anthracene (3). When the as-prepared sample was evacuated, the 3ꢀ2(AgOTf) framework retains
its original structure with a void space into which guest molecules such as acetone and benzene can be
restored.
Ó 2008 Elsevier Ltd. All rights reserved.
Self-assembly of metal ions and bridging ligands has gained
much attention because of the production of many interesting por-
ous solids which can entrap guest molecule.1 In the heart of this
synthetic approach, the design and use of pertinent organic linkers
play a key role because they are essential in preparing a variety of
supramolecular assemblies with metal ions. Among many possible
functional groups such as pyridyl, carboxylate, sulfide, and phos-
phates, the –CN on the aromatic ring has proved to be especially
versatile for the self-assembly of Ag-supramolecular architec-
tures.2 Once the cyano group is chosen as a metal-binding group,
the next step is to determine a suitable aromatic motif to which
the cyano group is introduced. We have targeted a bis(resorcinol)
derivative of anthracene (1), which can form a 2D network through
hydrogen bonds between terminal hydroxyl groups of the bis(res-
orcinol) groups.3 The large aromatic spacer of 1 acts as a part of the
framework wall in the de novo building block in making new coor-
dination architecture which has huge cavities capable of binding
many guest molecules. The guest incorporation capability of 1
can be enlarged if other phenyl units are inserted into the main
skeleton of 1 as demonstrated recently by us.4
the anthracene nucleus. In this contribution, we report a self-
assembly system of Ag(I)-coordination supramolecular architec-
ture based on 9,10-bis(3,5-dicyano-1-phenyl)anthracene (3). This
new ligand has two dicyanophenyl groups at both sides of an
anthracene moiety, and hence acts as a four connector when com-
bined with silver triflate (AgOTf) to produce a two-dimensional
extended network, 3ꢀ2(AgOTf).
The phenycyanol anthracene derivative (3) was made by treat-
ing 2 with KCN in the presence of tris(dibenzylideneacetone)–
dipalladium(0) chloroform (Pd2(dba)3(CHCl3)) and 1,10-bis(diphen-
ylphosphino)ferrocene (dppf) adducts (Scheme 1).6,7 The metal
complex 3ꢀ2(AgOTf) was obtained in mixing of acetone containing
3 and silver trifluoromethane sulfonate by light shielding for
1 week. The obtained crystal is yellow and very stable in a couple
of organic solvents such as benzene, acetone, and ethyl acetate
(orthorhombic, space group P212121).8 Figure 1 shows the X-ray
crystal structure of 3ꢀ2(AgOTf)ꢀ2(acetone), where anthracene unit
made orthogonal crossed structure with adjacent benzene ring,
which can catch silver metal cation by coordination bond through
cyano groups of anthracene. It means that the fundamental struc-
ture of cyano–silver–cyano unit (–CNꢀ ꢀ ꢀAgꢀ ꢀ ꢀNC–) was formed. It
was recognized that four units of 3ꢀ2(AgOTf)ꢀ2(acetone) assembled
together, which resulted in a formation of big cavity. The longitu-
dinal and lateral direction sizes of the cavity are 17.214 and
16.828 Å, respectively. It was shown that two acetone molecules
and two triflate anions were captured in the cavity. The distance
between oxygen of acetone and silver was 3.100 and 3.176 Å and
the oxygen of triflurate and silver was 2.594 and 2.659 Å, respec-
tively. As shown in Figure 2, it was recognized that cancellous
sheet with two dimensions was formed, where these sheets get
lined up back and forth. It was also indicated that these sheets take
If the resorcinol groups are replaced by other groups, the organ-
ic linker can be used as a building block in making new coordina-
tion architecture instead of hydrogen bond networks. One example
is a coordination polymer assembled by Cd2+ and 5-(9-anthrace-
nyl)pyrimidine, which was reported by Aoyama and co-workers a
long time ago.5 The produced network was 1D coordination poly-
mer because the pyrimidyl group was introduced at one side of
* Corresponding author. Tel.: +81 18 889 2440; fax: +81 18 837 0404.
E-mail address: hamada@ipc.akita-u.ac.jp (F. Hamada).
0040-4039/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2008.10.044

7362
K. Akimoto et al. / Tetrahedron Letters 49 (2008) 7361–7363
HO
HO
OH
OH
TfO
TfO
NC
NC
OTf
OTf
CN
CN
Tf2O
2.6-lutidine
CH2Cl2
1
2
3
KCN
cat.Pd2(dba)3(CHCl3)
dppf
CH3CN
Scheme 1. Preparations of 2 and 3 from 1.
observed value
Ag
3.100
Ag
Ag
17.214
3.176
2.659
Ag
Ag
16.828
2.594
Ag
theoretical value
Ag
Figure 1. The fragment of one 3ꢀ2(AgOTf)ꢀ2(acetone) layer is drawn using a stick
model. Two OTf anions and two acetone molecules reside in the cavity provided by
four Ag ions and four 3 ligands.
10
20
30
40
50
60
5
Figure 3. Two XRD patterns for the simulated and evacuated samples are presented
and compared.
place with doing a one-eighty, which resulted in the formation of a
deep vacant cavity. During the formation of sheets,
p–p interac-
tions (edge to edge) were observed at the benzene ring in 3, of
which the distance was 3.513 Å. The side and top views show
two sheets lay on running parallel and dogleg shapes of two
dimensional sheet structure, respectively. On investigationl a
different nature between 1 and 3ꢀ2(AgOTf)ꢀ2(acetone) crystals
was observed, and it was recognized that 3ꢀ2(AgOTf)ꢀ2(acetone)
crystal might be staunch because it was made from
–
CNꢀ ꢀ ꢀAgꢀ ꢀ ꢀNC– coordination bonded architecture.
Figure 2. Two 3ꢀ2(Ag) layers are drawn with green and red colors, while the OTf anions are depicted with the default atomic colors. The included acetone molecules have
been omitted in order to show the void space clearly.

K. Akimoto et al. / Tetrahedron Letters 49 (2008) 7361–7363
7363
Acetone
3
2
1
0
3
2
1
0
Benzene
desorption
adsorption
desorption
adsorption
0
0.2
0.4
0.6 0.8
P/Ps
1
0
0.2
0.4
0.6 0.8
P/Ps
1
Figure 4. Acetone and benzene adsorption isotherms measured up to a respective vapor pressure, Ps at 298 K. The as-prepared sample, 3ꢀ(2AgOTf)ꢀ2(acetone) was fully
evacuated to remove the occluded acetone molecules before the measurements.
8230; (e) Zhang, J.-J.; Zhou, H.-J.; Lachgar, A. Angew. Chem., Int. Ed. 2007, 46,
4995.
when the guest molecules are excluded, a powder X-ray structure
2. (a) Dong, Y.-B.; Ma, J.-P.; Huang, R.-Q.; Smith, M. D.; zur Loye, H.-C. Inorg. Chem.
In order to examine whether the crystal cavity is in exists or not
analysis was done. Single crystal of 3ꢀ2(AgOTf)ꢀ2(acetone) was
2003, 42, 294; (b) Dong, Y.-B.; Cheng, J.-Y.; Huang, R.-Q.; Smith, M. D.; zur Loye,
H.-C. Inorg. Chem. 2003, 42, 5699; (c) Wei, K.-J.; Ni, J.; Gao, J.; Liu, Y.; Liu, Q.-L.
Eur. J. Inorg. Chem. 2007, 3868; (d) Hirsch, K. A.; Wilson, S. R.; Moore, J. S. Chem.
Commun. 1998, 13; (e) Raehm, L.; Mimassi, L.; Guyard-Duhayon, C.; Amouri, H.
dried to remove the acetone at 60 °C in vacuo to give acetone-free
apohost 3ꢀ2(AgOTf). As shown in Figure 3, it was recognized that
the existence of the same peaks of theoretical figures were con-
firmed. It means that the structure of 3ꢀ2(AgOTf) was rigid because
the cavity remained in existence when guests were excluded. To
investigate the capability of adsorption for guest molecules, vapor
adsorption analysis for apohost was done. The isotherm measure-
ments for acetone or benzene were performed at 298 K by using an
automatic volumetric adsorption apparatus (BELSORP 18SP-V; BEL
Inc). It was recognized that 50 mL of acetone and 30 mL of benzene
were absorbed per 1.0 g of apohost, respectively. It means that
apohost adsorbed 2 acetone molecules and 1 benzene molecule
per apohost complex, respectively. It was suggested that the differ-
ence of adsorption behavior between acetone and benzene was
dependent on these molecular sizes. At the first stage of an absorp-
tion near the 0 of P/Ps, it shows that the 1 acetone molecule and 0.5
benzene molecule were captured in the cavity of the apohost, as
shown in Figure 4. The curve of absorption isotherm indicates that
the cavity of apohost continued to exist under the guest-free situ-
ation. It means that apohost has the same size cavity under all
conditions.
In this study, tetraphenylcyano derivative of anthracene (3) has
been successfully prepared by the reaction of tetra triflates of
bis(resorcinol) derivative of anthracene (2) treated with KCN. In
the complex, 3ꢀ2(AgOTf)ꢀ2(acetone) system gets 2D cancellous
structure, where cyano groups make coordination linkage with
Ag (I) resulting in making a hole structure. On investigation by
using X-ray powder diffraction and vapor adsorption analysis,
it was recognized that apohost is keeping whole structure even
on the guest-free situation. The hole size is capable to adsorb 2
acetone molecules per 3ꢀ2(AgOTf) complex.
Inorg. Chem. 2003, 42, 5654; (f) Moussa, J.; Guyard-Duhayon, C.; Boubekeur, K.;
Amouri, H.; Yip, S.-K.; Yam, V. W. W. Cryst. Growth Des. 2007, 7, 962; (g) Moussa,
J.; Boubekeur, K.; Amouri, H. Eur. J. Inorg. Chem. 2005, 3808; (h) Mimassi, L.;
Guyard-Duhayon, C.; Raehm, L.; Amouri, H. Eur. J. Inorg. Chem. 2002, 2453.
3. (a) Kobayashi, K.; Endo, K.; Aoyama, Y.; Masuda, H. Tetrahedron Lett. 1993, 34,
7929; (b) Kobayashi, K.; Koyanagi, M.; Endo, K.; Masuda, H.; Aoyama, Y. Chem.
Eur. J. 1998, 4, 417; (c) Endo, K.; Sawaki, T.; Koyanagi, M.; Kobayashi, K.; Masuda,
H.; Aoyama, Y. J. Am. Chem. Soc. 1995, 117, 8341; (d) Tanaka, T.; Endo, K.;
Aoyama, Y. Chem. Lett. 2000, 1424; (e) Sawaki, T.; Aoyama, Y. J. Am. Chem. Soc.
1999, 121, 4769; (f) Tanaka, T.; Endo, K.; Aoyama, Y. Bull. Chem. Soc. Jpn. 2001, 74,
907; (g) Endo, K.; Koike, T.; Sawaki, T.; Hayashida, O.; Masuda, H.; Aoyama, Y. J.
Am. Chem. Soc. 1997, 119, 4117.
4. Akimoto, K.; Suzuki, H.; Kondo, Y.; Endo, K.; Akiba, U.; Aoyama, Y.; Hamada, H.
Tetrahedron 2007, 63, 6887.
5. Ezuhara, T.; Endo, K.; Aoyama, Y. J. Am. Chem. Soc. 1999, 121, 3279.
6. Preparation of triflate derivative of 9,10-bis(3,5-dihydroxyl-1-phenyl)anthracene
(2): To a CH2Cl2 solution (300 mL) containing 1 (3.24 g, 8.25 mol) cooled in ice
bath, 2,6-lutidine (19.06 mL, 80.25 mmol) and trifluoromethane sulfonic
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 extracted with chloroform. The chloroform layer was washed with
water, saturated copper sulfate solution, water, and saturated saline. The
organic layer was dried over Na2SO4, and filtered, evaporated to crude product,
which was then washed with ethanol and filtered to give a triflate derivative
9,10-bis(3,5-dihydroxyl-1-phenyl) anthracene (6.77 g, 89% yield). 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, antharcene-H).
7. Preparation of cyano derivative of 9,10-bis(3,5-dihydroxyl-1-phenyl)anthracene
(3): To a solution of 50 mL of CH3CN containing 2 (4.32 g, 4.70 mmol), tris-
(dibenzylideneacetone)-dipalladium(0)chloroform
adduct
(0.389 g,
0.380 mmol), 1,10-bis(diphenylphosphino)ferrocene (0.844 g, 1.50 mmol), KCN
(2.59 g, 40.0 mmol) were added. The reaction mixture was stirred at 50 °C for
24 h. Then, the reaction mixture was concentrated to remove organic solvents
and extracted with chloroform. The organic layer was concentrated under
reduced pressure to give oily residue, which was treated with activated carbon
filtration, and then purified with alumina flash column chromatography. Elution
with chloroform gave fractions containing corresponding product, which was
concentrate to remove solvents and the resulting product was treated with a p-
xylene to give 3 (1.85 g, 92.2% yield) as precipitates. 1H NMR (300 MHz, DMSO-
d6): d 7.54 (s, 8H, phenyl-H), 8.34 (d, 4H, phenyl-H), 8.74 (s, 2H, anthracene-H).
13C NMR (75 MHz, DMSO-d6/CDCl3): d 113.9(s), 117.3(s), 126.2(s), 126.9(s),
129.2(s), 133.8(s), 136.2(s), 139.0(s), 140.6(s). IR (KBr): 2234 cmꢁ1 (–CN).
8. Crystal data: C38H26Ag2F6N4O8S2, M = 1060.49, colorless, crystal dimensions
0.20 ꢂ 0.20 ꢂ 0.20 mm, orthorhombic, space group P212121, a = 26.3733(8),
Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.tetlet.2008.10.044.
b = 8.75662(2),
radiation Dcalcd = 1.772 g cmꢁ3
(Mo K
) = 1.173 cmꢁ1, data collections using Rigaku RAXIS-RAPID imaging
plate diffractometer, 44260 measured reflections, 30980 unique reflections
(Rint = 0.059), 4950 observed reflections (I > 2.00 (I)), 522 parameters,
c = 17.2143(6) Å,
V = 39755.5(5) Å3,
Z = 4,
Mo
Ka
,
T = 163.2 K, numerical absorption correction,
References and notes
l
a
r
1. (a) Wei, K.-J.; Ni, J.; Gao, J.; Liu, Y.; Liu, Q.-L. Eur. J. Inorg. Chem. 2007, 3868; (b)
Moussa, J.; Amouri, H. Angew. Chem., Int. Ed. 2008, 47, 1372; (c) D’Souza, F.; El-
Khouly, M. E.; Gadde, S.; Zandler, M. E.; McCarty, A. L.; Araki, Y.; Ito, O.
Tetrahedron 2006, 62, 1967; (d) Park, Y. K.; Choi, S. B.; Kim, H.; Kim, K.; Won, B.-
H.; Choi, K.; Choi, J.-S.; Ahn, W.-S.; Won, N.; Kim, S.; Jung, D. H.; Choi, S.-H.; Kim,
G.-H.; Cha, S.-S.; Jhon, Y. H.; Yang, J. K.; Kim, J. Angew. Chem., Int. Ed. 2007, 46,
R = 0.0809, wR = 0.1623, refined against |F|, GOF = 1.6947. All crystallographic
data of these crystals have been deposited at the Cambridge Crystallographic
Data Center in CIF format CCDC No. 690241. 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).