Crystal Growth & Design
ARTICLE
The emissions of 1 and 2 are probably due to the chelation of the
ligand to the metal center, which may result in πL f ns ligand-to-
metal charge transfer (LMCT).27 The coordination enhances the
“rigidity” of the ligand and thus reduces the loss of energy
through a radiationless pathway, which facilitates the πLfπL*
transitions. The difference in photoluminescence spectra of 1
and 2 may be attributed to the different coordination environ-
ments of the Zn(II) and crystal packing in the solid state.
Gas Adsorption Properties. X-ray crystal structure and
thermal studies show that complexes 1ꢀ4 possess the micro-
porous structure with removable guest molecules in open
channels. These complexes may serve as potential gas adsorp-
tion/separation materials. To investigate their porosity, the
nitrogen adsorption measurements at 77 K were performed.
Prior to the measurements, all the samples were activated by
using the procedure described by Zhou.28 As depicted in
Figure 14, complexes 1, 2, and 4 showed permanent porosity,
while 3 exhibited no measurable adsorption for N2 gas. It is not
surprising because of the lack of free solvent accessible voids in 3
as calculated by PLATON.21 All the N2 adsorption isotherms of
1, 2 and 4 are of type III, indicating the weak interactions
between nitrogen molecules and the host frameworks. The
hystereses between adsorption and desorption isotherms of 1,
2 and 4 are probably due to the retaining of N2 in the flexible
small channels as a result of pore opening comparable to the size
of N2 molecule. The BrunauerꢀEmmettꢀTeller (BET) surface
areas are calculated from N2 adsorption isotherms to be 216, 117,
and 53 m2/g, respectively.
’ REFERENCES
(1) (a) Farha, O. K.; Malliakas, C. D.; Kanatzidis, M. G.; Hupp, J. T.
J. Am. Chem. Soc. 2009, 132, 950. (b) Kitagawa, S.; Kitaura, R.; Noro, S.
Angew. Chem., Int. Ed. 2004, 43, 2334. (c) Li, J. R.; Kuppler, R. J.; Zhou,
H. C. Chem. Soc. Rev. 2009, 38, 1477. (d) Ma, S.; Zhou, H. C. Chem.
Commun. 2009, 46, 44. (e) Rosi, N. L.; Eckert, J.; Eddaoudi, M.; Vodak,
D. T.; Kim, J.; O’Keeffe, M.; Yaghi, O. M. Science 2003, 300, 1127. (f)
Yaghi, O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.;
Kim, J. Nature 2003, 423, 705. (g) Zhang, J. P.; Chen, X. M. J. Am. Chem.
Soc. 2009, 131, 5516. (h) Chen, B.; Xiang, S.; Qian, G. Acc. Chem. Res.
2010, 43, 1115.
(2) (a) Chen, X. D.; Wu, H. F.; Zhao, X. H.; Zhao, X. J.; Du, M. Cryst.
Growth Des. 2006, 7, 124. (b) Liu, J. Q.; Wang, Y. Y.; Zhang, Y. N.; Liu,
P.; Shi, Q. Z.; Batten, S. R. Eur. J. Inorg. Chem. 2009, 2009, 147. (c)
Withersby, M. A.; Blake, A. J.; Champness, N. R.; Cooke, P. A.;
Hubberstey, P.; Li, W. S.; Schroder, M. Inorg. Chem. 1999, 38, 2259.
(d) Hirotsu, M.; Kuwamura, N.; Kinoshita, I.; Kojima, M.; Yoshikawa,
Y.; Ueno, K. Dalton Trans. 2009, 7678. (e) Du, J. L.; Hu, T. L.; Li, J. R.;
Zhang, S. M.; Bu, X. H. Eur. J. Inorg. Chem. 2008, 2008, 1059. (f) Fang,
R. Q.; Zhang, X. M. Inorg. Chem. 2006, 45, 4801. (g) Cui, F. Y.; Huang,
K. L.; Xu, Y. Q.; Han, Z. G.; Liu, X.; Chi, Y. N.; Hu, C. W. CrystEngComm
2009, 11, 2757.
(3) (a) Eddaoudi, M.; Moler, D. B.; Li, H.; Chen, B.; Reineke, T. M.;
O’Keeffe, M.; Yaghi, O. M. Acc. Chem. Res. 2001, 34, 319. (b) Perry, J. J.,
IV; Perman, J. A.; Zaworotko, M. J. Chem. Soc. Rev. 2009, 38, 1400.
(4) Zang, S.; Su, Y.; Li, Y.; Ni, Z.; Meng, Q. Inorg. Chem. 2005,
45, 174.
(5) (a) Sun, L. X.; Qi, Y.; Wang, Y. M.; Che, Y. X.; Zheng, J. M.
CrystEngComm 2010, 12, 1540. (b) Wang, X. L.; Qin, C.; Wang, E. B.;
Xu, L. Eur. J. Inorg. Chem. 2005, 2005, 3418.
(6) (a) Zang, S.; Su, Y.; Li, Y. Z.; Lin, J.; Duan, X.; Meng, Q.; Gao, S.
CrystEngComm 2009, 11, 122. (b) Zang, S.; Su, Y.; Duan, C.; Li, Y.;
Zhou, H.; Meng, Q. Chem. Commun. 2006, 48, 4997.
’ CONCLUSIONS
(7) (a) Su, Y.; Zang, S.; Li, Y.; Zhou, H.; Meng, Q.; Gao, S. Cryst.
Growth Des. 2007, 7, 1277. (b) Zang, S.; Su, Y.; Song, Y.; Li, Y.; Ni, Z.;
Zhou, H.; Meng, Q. Cryst. Growth Des. 2006, 6, 2369.
(8) Cairns, A. J.; Perman, J. A.; Wojtas, L.; Kravtsov, V. C.; Alkordi,
M. H.; Eddaoudi, M.; Zaworotko, M. J. J. Am. Chem. Soc. 2008, 130, 1560.
(9) (a) Chen, B.; Ockwig, N. W.; Millward, A. R.; Contreras, D. S.;
Yaghi, O. M. Angew. Chem., Int. Ed. 2005, 44, 4745. (b) Chen, B.;
Ockwig, N. W.; Fronczek, F. R.; Contreras, D. S.; Yaghi, O. M. Inorg.
Chem. 2005, 44, 181.
(10) (a) Lin, X.; Jia, J.; Zhao, X.; Thomas, K. M.; Blake, A. J.; Walker,
G. S.; Champness, N. R.; Hubberstey, P.; Schr€oder, M. Angew. Chem., Int.
Ed. 2006, 45, 7358. (b) Lin, X.; Telepeni, I.; Blake, A. J.; Dailly, A.;
Brown, C. M.; Simmons, J. M.; Zoppi, M.; Walker, G. S.; Thomas, K. M.;
Mays, T. J.; Hubberstey, P.; Champness, N. R.; Schr€oder, M. J. Am.
Chem. Soc. 2009, 131, 2159.
(11) (a) Yang, S.; Lin, X.; Blake, A. J.; Walker, G. S.; Hubberstey, P.;
Champness, N. R.; Schr€oder, M. Nat. Chem. 2009, 1, 487. (b) Yang, S.;
Lin, X.; Dailly, A.; Blake, A. J.; Hubberstey, P.; Champness, N. R.;
Schr€oder, M. Chem.—Eur. J. 2009, 15, 4829.
Four new metalꢀorganic coordination polymers of Zn(II)
and Mn(II) were solvothermally synthesized by using a quad-
ricarboxylate ligand. The formation of the four complexes is
strongly dependent on the solvent and metals used during the
synthesis. The four complexes possess interesting topological
structures, three of which have permanent porosity. The ligand in
these complexes exhibits rich coordination chemistry owing to its
semirigid flexibility. This study shows that using semirigid multi-
dentate ligands in combination of control of synthetic parameters
such as solvents and metals could lead to new compounds with
interesting structures and properties.
’ ASSOCIATED CONTENT
S
Supporting Information. Crystallographic information
b
(cif) files, XRPD, and tables for interatomic distances and
angles. This material is available free of charge via the Internet
(12) Qiu, W.; Perman, J. A.; Wojtas, L.; Eddaoudi, M.; Zaworotko,
M. J. Chem. Commun. 2010, 46, 8734.
(13) Pan, Z.; Zheng, H.; Wang, T.; Song, Y.; Li, Y.; Guo, Z.; Batten,
S. R. Inorg. Chem. 2008, 47, 9528.
’ AUTHOR INFORMATION
(14) (a) Ren, S. B.; Zhou, L.; Zhang, J.; Zhu, Y. L.; Du, H. B.; You,
X. Z. CrystEngComm 2010, 12, 1635. (b) Ren, S. B.; Zhou, L.; Zhang, J.;
Du, H. B.; You, X. Z. CrystEngComm 2009, 11, 1834. (c) Liang, L. L.;
Ren, S. B.; Zhang, J.; Li, Y. Z.; Du, H. B.; You, X. Z. Cryst. Growth Des.
2010, 10, 1307. (d) Zhang, J.; Xue, Y. S.; Liang, L. L.; Ren, S. B.; Li, Y. Z.;
Du, H. B.; You, X. Z. Inorg. Chem. 2010, 49, 7685.
(15) (a) Liang, L. L.; Ren, S. B.; Wang, J.; Zhang, J.; Li, Y. Z.; Du,
H. B.; You, X. Z. CrystEngComm 2010, 12, 2669. (b) Liang, L. L.; Zhang,
J.; Ren, S. B.; Ge, G. W.; Li, Y. Z.; Du, H. B.; You, X. Z. CrystEngComm
2010, 12, 2008. (c) Liang, L. L.; Ren, S. B.; Zhang, J.; Li, Y. Z.; Du, H. B.;
You, X. Z. Dalton Trans. 2010, 39, 7723.
Corresponding Author
*E-mail: hbdu@nju.edu.cn.
’ ACKNOWLEDGMENT
We are grateful for financial support from the National Basic
Research Program (2011CB808704 and 2007CB925101) and
the National Natural Science Foundation of China (21021062
and 20931004).
2451
dx.doi.org/10.1021/cg200229h |Cryst. Growth Des. 2011, 11, 2444–2452