Professional Documents
Culture Documents
4
anions incorporated [10]. Polycarboxylates
have been extensively used as organic linkers to bind metal
1387-7003/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2006.07.041
*
Corresponding author. Tel.: +886 5 2428168; fax: +886 5 2721040
E-mail address: chejhl@ccu.edu.tw (J.-H. Liao).
www.elsevier.com/locate/inoche
Inorganic Chemistry Communications 9 (2006) 12271231
centers to form a variety of open frameworks [11].
Recently, we have published the ionothermal synthesis of
(EMIM)[Cd(BTC)] (EMIM = 1-ethyl-3-methylimidazo-
lium, BTC = 1,3,5-benzenetricarboxylate), with a 3D anio-
nic framework and imidazolium cations as counterions
[12]. We have been continuing to explore the ionothermal
synthesis of polycarboxylate-based metal-organic frame-
works, to investigate the feasibility of using ionic liquids
as common reaction media.
Here we report the ionothermal synthesis of a two-
dimensional (2D) metal-organic framework: (BMIM)
2
-
[Cd
3
(BDC)
3
Br
2
], which exhibits intense blue luminescence.
In this experiment, the ionic liquid, 1-butyl-3-methylimi-
dazolium bromide, was prepared under microwave radia-
tion [13]. The starting reagents, Cd(NO
3
)
2
4H
2
O and
1,4-benzenedicarboxylic acid, in a 3:1 ratio, dissolved com-
pletely in the ionic liquids, forming a clear colorless viscous
solution at 160 C. It was kept for 15 days until many
colorless crystals formed [14]. The stoichiometric ratio
did not give any solid-state product. The products are
not stable in water but are stable in alcohol and acetone.
Thermogravimetric and dierential thermal analyses indi-
cate 1 is stable up to ca. 340 C, following by an abrupt
endothermic weight loss owing to the collapse of the 2D
framework. The identity of the bulk product is conrmed
by elemental analysis, and by comparing the experimental
and simulated X-ray powder diraction patterns. The crys-
tal structure of 1 has been characterized by single-crystal
X-ray diraction analysis, [15] which reveals that 1 con-
tains an anionic 2D framework built by cross-linking tri-
meric Cd
3
O
12
Br
2
units with BDC ligands (Fig. 1). Each
Cd
3
trimer is composed of a CdO
6
octahedron, sitting at
a centre of inversion, sandwiched by two distorted CdO
5
Br
octahedra (d(Cd Cd) = 3.5882(3) A
) in an edge-sharing
fashion. Each Cd
3
trimeric unit is surrounded by six BDC
ligands, extending into a 2D network, which contains trian-
gular meshes with three edges of 10.29 A
10.29 A
10.30 A
2n
n
layers are per-
pendicular to the (100) crystallographic direction. Termi-
nal Cd-Br bonds are found to point toward the
interlayered space, with the partially negatively charged
Br atoms interacting with the positively charged aromatic
rings of imidazolium cations. Interestingly, the 2D
Cd
3
BDC
3
Br
2
2n
n
anionic framework of 1 is closely
related to the neutral [Zn
3
(BDC)
3
(H
2
O)
2
]
n
framework in
[Zn
3
(BDC)
3
(H
2
O)
2
] 4DMF [16], in which terminal Zn
OH
2
bonds point toward the interlayered space, where
DMF solvent molecules are located. It has been reported
the aromatic CH X
hydrogen bonding
interactions (d(C Br) = 3.927(5) A
2n
n
network, viewed down the a-axis. (b) The packing diagram of (BMIM)
2
[Cd
3
(BDC)
3
Br
2
]. The carbon
atoms of imidazolium cations are illustrated in purple for clarity. (For interpretation of the references to color in this gure legend, the reader is referred to
the web version of this article.)
200 250 300 350 400 450 500
(b)
(a)
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
wavelength (nm)
Fig. 3. Optical spectra of (BMIM)
2
[Cd
3
(BDC)
3
Br
2
]: (a) Diuse reectance
absorption spectrum (in red). (b) Emission spectrum with k
ex
= 265 nm (in
blue). (For interpretation of the references to color in this gure legend,
the reader is referred to the web version of this article.)
J.-H. Liao, W.-C. Huang / Inorganic Chemistry Communications 9 (2006) 12271231 1229
wavelength by metal coordination [21]. The emission spec-
trum (k
ex
= 265 nm), (Fig. 3b), shows a strong band at
359 nm, which can be assigned as ligand to metal charge
transfer [22]; as well as a weak band at 390 nm and a strong
band at 432 nm, which can be assigned as the combination
of BDC and BMIM emission [20]. The weak band at
460 nm is believed to arise from BDC, which also gives a
weak band at 460 nm in the emission spectrum of free
H
2
BDC.
In summary, this work demonstrates that ionic liquids,
potential environmentally benign reaction media, can be
used in the solid state synthesis and crystallization of
metal-organic frameworks, in the temperature regime
where organic species can be incorporated. In the structure
of the title compound, coordinative Br
anions, originated
from ionic liquids, are incorporated into the extended
framework. This can be avoided by the choice of ionic liq-
uids containing less-coordinating counter anions. The imi-
dazolium cations are located in the void space of the
coordination polymeric framework. This implies that the
cations of the organic molten salts can be used as potential
structure-directing templates for the crystal engineering of
porous coordination polymers. In addition, the title com-
pound exhibits blue emission and may be applied as a
potential photoactive material.
Acknowledgements
The authors acknowledge the National Science Council
of Taiwan for nancial support. We also thank Professor
Biing-Chiau Tzeng for helpful discussions on emission
spectroscopy.
Appendix A. Supplementary data
Experimental details, TGA, XRPD patterns and IR
spectrum are available in electronic supplementary infor-
mation. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.inoche.2006.07.041.
References
[1] (a) M. Eddaoudi, D.B. Moler, H. Li, B. Chen, T.M. Reineke, M.
OKeee, O.M. Yaghi, Acc. Chem. Res. 34 (2001) 319;
(b) B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629;
(c) R. Matsuda, R. Kitaura, S. Kitagawa, Y. Kubota, R.V.
Belosludov, T.C. Kobayashi, H. Sakamoto, T. Chiba, M. Takata,
Y. Kawazoe, Y. Mita, Nature 436 (2005) 238;
(d) O.R. Evans, W. Lin, Acc. Chem. Res. 35 (2002) 511.
[2] (a) T. Welton, Chem. Rev. 99 (1999) 2071;
(b) J. Dupont, R.F. de Souza, P.A.Z. Suarez, Chem. Rev. 102 (2002)
3667;
(c) N. Audic, H. Clavier, M. Mauduit, J.C. Guillemin, J. Am. Chem.
Soc. 125 (2003) 9248;
(d) W. Lu, A.G. Fadeev, B.H. Qi, E. Smela, B.R. Mattes, J. Ding,
G.M. Spinks, J. Mazurkiewicz, D.Z. Zhou, G.G. Wallace, D.R.
MacFarlane, S.A. Forsyth, M. Forsyth, Science 297 (2002) 983;
(e) P. Wang, S.M. Zakeeruddin, P. Comte, I. Exnar, M. Gratzel, J.
Am. Chem. Soc. 125 (2003) 1166.
[3] (a) P. Bonho te, A.-P. Dias, N. Papageorgiou, K. Kalyanasundaram,
M. Gratzel, Inorg. Chem. 35 (1996) 1168;
(b) D. Camper, P. Scovazzo, C. Koval, R. Noble, Ind. Eng. Chem.
Res. 43 (2004) 3049;
(c) K.E. Gutowski, G.A. Broker, H.D. Willauer, J.G. Huddleston,
R.P. Swatloski, J.D. Holbrey, R.D. Rogers, J. Am. Chem. Soc. 125
(2003) 6632;
(d) J. Homann, M. Nu chter, B. Ondruschka, P. Wasserscheid,
Green Chem. 5 (2003) 296.
[4] R.D. Rogers, K.R. Seddon, Science 302 (2003) 792.
[5] (a) R.P. Swatloski, J.D. Holbrey, R.D. Rogers, Green Chem. 5 (2003)
361;
(b) R.P. Swatloski, J.D. Holbrey, S.B. Memon, G.A. Caldwell, K.A.
Caldwell, R.D. Rogers, Chem. Commun. (2004) 668.
[6] (a) C.S. Cundy, P.A. Cox, Chem. Rev. 103 (2003) 663;
(b) R.E. Morri, S.J. Weigel, Chem. Soc. Rev. 26 (1997) 309.
[7] (a) H. Shi, Y. Shan, M. He, Y. Liu, J. Solid State Chem. 176 (2003)
33;
(b) E.R. Cooper, C.D. Andrews, P.S. Wheatley, P.B. Webb, P.
Wormald, R.E. Morris, Nature 430 (2004) 1012;
(c) J.H. Liao, P.C. Wu, Y.H. Bai, Inorg. Chem. Commun. 8 (2005)
390;
(d) E.R. Parnham, R.E. Morris, J. Am. Chem. Soc. 128 (2006) 2204;
(e) E.R. Parnham, P.S. Wheatley, R.E. Morris, Chem. Commun.
(2006) 380;
(f) C.Y. Sheu, S.F. Lee, K.H. Lii, Inorg. Chem. 45 (2006) 1891.
[8] (a) K. Yoo, H. Choi, D.D. Dionysiou, Chem. Commun. (2004)
2000;
(b) Y. Zhou, M. Antonietti, J. Am. Chem. Soc. 125 (2003) 14960;
(c) H. Itoh, K. Naka, Y. Chujo, J. Am. Chem. Soc. 126 (2004)
3026;
(d) W.W. Wang, Y.J. Zhu, Cryst. Growth Des. 5 (2005) 505;
(e) Y. Jiang, Y.J. Zhu, J. Phys. Chem. B 109 (2005) 4361.
[9] (a) S.I. Zones, Zeolites 9 (1989) 458;
(b) C.J. Adams, A.E. Bradley, K.R. Seddon, Aust. J. Chem. 54 (2001)
679.
[10] (a) K. Jin, X. Huang, L. Pang, J. Li, A. Appel, S. Wherland, Chem.
Commun. (2002) 2872;
(b) D.N. Dybtsev, H. Chun, K. Kim, Chem. Commun. (2004)
1594.
[11] J. Kim, B. Chen, T.M. Reineke, H. Li, M. Eddaoudi, D.B. Moler, M.
Okeee, O.M. Yaghi, J. Am. Chem. Soc. 123 (2001) 8239.
[12] J.H. Liao, P.C. Wu, W.C. Huang, Cryst. Growth Des. 5 (2006) 1062.
[13] R.S. Varma, V.V. Namboodiri, Chem. Commun. (2001) 643.
[14] Cd(NO
3
)
2
4H
2
O (0.463 g, 1.5 mmol) and 1,4-benzenedicarboxylic
acid (0.083 g, 0.5 mmol), in a ratio of 3:1, were dissolved in 1.0-g 1-
butyl-3-methylimidazolium bromide, forming a clear viscous solution.
The mixture was kept at 160 C for 5 days until many chunky
colourless crystals of 1 were observed. 0.151-g crystals (71% yield,
based on BDC) were collected after ltration and several washings
with methanol. IR(KBr, cm
1
): 3450(br), 3144(w), 3104(m), 3087(sh),
2958(m), 2931(w), 2872(w), 1958(w), 1599(sh), 1569(s), 1503(m),
1384(s), 1314(m), 1261(w), 1168(m), 1108(w), 1089(w), 1013(m),
1089(w), 1013(m), 886(w), 840(s), 744(s), 648(w), 618(w), 525(s),
442(w). Anal. Calcd for C
40
H
42
N
4
O
12
Br
2
Cd
3
: C, 37.89; H, 3.31; N,
4.42. Found: C, 37.20; H, 3.32; N, 4.01.
[15] Crystal data (Bruker Smart Apex CCD diractometer, Mo Ka
radiation, 298 K): C
40
H
42
N
4
O
12
Br
2
Cd
3
, M = 1267.80, monoclinic
P2
1
/c (No. 14), a = 13.6661(8) A
, b = 10.2967(6) A
, c = 17.8289(10)
A
, b = 110.2460(10), V = 2353.8(2) A
3
, Z = 4, q
calcd.
= 1.798 g
cm
1
, l = 3.101 mm
1
, 20441 reections collected, 5692 independent
(R
int
= 0.0210), 279 parameters, R
1
= 0.0288 for 5692 observed
reections with I > 2r(I) (0.0357 for all data), wR
2
= 0.0730,
S = 1.038, max. Dq = 0.696 e A
3
. CCDC 604597.
[16] M. Edgar, R. Mitchell, A.M.Z. Slawin, P. Lightfood, P.A. Wright,
Chem. Eur. J. 7 (2001) 5168.
[17] (a) A. Elaiwi, P.B. Hitchcock, K.R. Seddon, N. Srinivasan, Y.M.
Tan, T. Welton, J.A. Zora, J. Chem. Soc., Dalton Trans. (1995) 3467;
1230 J.-H. Liao, W.-C. Huang / Inorganic Chemistry Communications 9 (2006) 12271231
(b) P.B. Hitchcock, K.R. Seddon, T. Welton, J. Chem. Soc., Dalton
Trans. (1993) 2639;
(c) A.K. Abdul-Sada, A.M. Greenway, P.B. Hitchcock, T.J. Moham-
med, K.R. Seddon, J.A. Zora, J. Chem. Soc. Chem. Commun. (1986)
1753;
(d) C.J. Dymek, D.A. Grossie, A.V. Fratini, W.W. Adams, J. Mol.
Struct. (1989) 25.
[18] G.B. Deacon, R.J. Phillips, Coord. Chem. Rev. 23 (1980) 227.
[19] (a) M. Koel, Proc. Estonian Acad. Sci. Chem. 49 (2000) 145;
(b) S.A. Katsyuba, P.J. Dyson, E.E. Vandyukova, A.V. Chernova, A.
Vidis Helv, Chim. Acta 87 (2004) 2556.
[20] B. Paul, B. Zimmermann, K.M. Fromm, C. Janiak, Z. Anorg, Allg.
Chem. 630 (2004) 1650.
[21] C. Janiak, J. Chem. Soc., Dalton Trans. (2003) 2781.
[22] J.C. Dai, X.T. Wu, S.M. Hu, Z.Y. Fu, J.J. Zhang, W.X. Du, H.H.
Zhang, R.Q. Sun, Eur. J. Inorg. Chem. (2004) 2096.
J.-H. Liao, W.-C. Huang / Inorganic Chemistry Communications 9 (2006) 12271231 1231