Inorganic Chemistry
Article
2−
distance of Nnitro···CCPMA of 3.091 Å. A close-up shot of the
interaction between nitrobenzene and one of CPMA2− ligands
incorporated in 1 is shown in Figure 5b. In this range of
interactions, the electron-deficient nitrobenzene can act as an
electron acceptor for the photoexcited electrons of 1, resulting
in electron transfer from the MOF to nitrobenzene, followed by
back electron transfer instead of fluorescence. Moreover, as
shown in the superimposed X-ray structures of 1 and
1⊃nitrobenzene (Figure 5c), π−π interactions cause the
molecular dynamics of the flexible ligand CPMA2−; meanwhile,
the methyl group of CPMA2− approaches the neighboring
benzene ring of CPMA2− to induce C−H···π interactions in the
framework. The Cmethyl···centroid distances decrease from 4.359
to 4.050 Å after nitrobenzene inclusion. This interligand
interaction also contributes to the change in the electronic
structure of 1, quenching the fluorescence.
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CONCLUSIONS
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In conclusion, we introduced a well-defined ditopic organic
ligand, H2CPMA, for the potential provision of the
luminescence properties in MOFs and the successful
preparation of the luminescent three-dimensional Li-based
MOF. A luminescent Li-based MOF detected explosive
nitroaromatic compounds selectively by showing an intensive
color change as well as luminescence quenching in the solid
state. We provided direct evidence for interaction sites in the
MOF toward the nitroaromatic compound via single-crystal
XRD of MOF containing nitroaromatic compounds. Strong
interaction between the MOF and included compounds
explained the alteration of the electronic structure of the
MOF. This result will afford in-depth understanding to help in
the design of MOFs as sensors, in which the specific sites to
interact with analytes are introduced.
ASSOCIATED CONTENT
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S
* Supporting Information
X-ray crystallographic files in CIF format, X-ray crystallographic
table, ORTEP drawing of 1, TGA trace of 1, XRD patterns of
Li-MOF 1 and dried MOF, gas-sorption isotherms of Li-MOF
1, photographs of 1 after immersion in various solvents, N 1s
XPS result of 1⊃nitrobenzene, UV/vis spectra of 1 and
1⊃nitrobenzene, fluorescence spectra of 1⊃DNT, and
concentration-dependent fluorescence spectra. This material is
AUTHOR INFORMATION
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Corresponding Author
(22) Rao, D.; Lu, T.; Xiao, C.; Kan, E.; Deng, K. Chem. Commun.
2011, 47, 7698−7700.
(23) Mulfort, K. L.; Hupp, J. T. J. Am. Chem. Soc. 2007, 129, 9604−
9605.
(H.R.M.). Tel: +82-52-217-2928. Fax: +82-52-217-2019.
Notes
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Growth Des. 2010, 10, 2801−2805. (c) Banerjee, D.; Kim, S. J.; Paries,
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J.; Borkowski, L. A.; Xu, W.; Paries, J. B. Cryst. Growth Des. 2010, 10,
709−715.
(25) (a) Abrahams, B. F.; Grannas, M. J.; Hudson, T. A.; Robson, R.
Angew. Chem., Int. Ed. 2010, 49, 1087−14089. (b) Liu, Y.-Y.; Zhang, J.;
Xu, F.; Sun, L.-X.; Zhang, T.; You, W.-S.; Zhao, Y.; Zeng, J.; Cao, Z.;
Yang, D. Cryst. Growth Des. 2008, 8, 3127−3129.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was supported by Basic Science Research Program
through the National Research Foundation of Korea funded by
the Ministry of Education, Science and Technology (Grants
2011-0004358 and 2012-002507). X-ray crystallography at the
PLS-II 2D SMC beamline was supported, in part, by MEST
and POSTECH.
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dx.doi.org/10.1021/ic3011458 | Inorg. Chem. 2013, 52, 589−595