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School of Material Science and Engineering, Anhui University of Science and Technology, Huainan 232001, China
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China
a r t i c l e
i n f o
Article history:
Received 23 September 2014
Received in revised form 3 December 2014
Accepted 8 December 2014
Available online 10 December 2014
Keywords:
Metalorganic framework
ReO3 net
Magnesium-containing cluster
Solvent effects
a b s t r a c t
Through changing the components of solvent, two Mg-based metalorganic frameworks were synthesized,
which possess the same two-fold interpenetrated ReO3 net constructed by identical linkers, 4,4,4-benzene1,3,5-triyl-tribenzoate, but distinct nodes, Mg2 and Mg6 units, respectively. Here, DMSO and water are key factors
for forming hexanuclear clusters, while DMF and DMSO act as template reagents for constructing
super-octahedral cavities.
2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.inoche.2014.12.012
1387-7003/ 2014 Elsevier B.V. All rights reserved.
42
Fig. 1. Views of the coordination sphere of Mg2+ ion and Mg2 unit in 1. Hydrogen atoms
have been omitted for clarity. Symmetry operations: c = x, y, z; d = x, y, z + 1;
e = x, y, z + 1.
Fig. 2. Views of (a) cage A and (b) cage B constructed by Mg2 units and BTB linkers in 1. (c) The mutual connection of eight cage As and the formation of a cage B, which indicates one
framework in 1. The large blue sphere represents the space inside cage A. Color scheme as follows: Mg (green spheres), O (red spheres), C (gray spheres), the stick model of BTB (blue
and gray).
43
Fig. 3. (a) Polyhedral representation of double interpenetrated structure for 1. The pink net is shifted to the blue one by the 1/2 1/2 1/2 translation. Each vertex of the polyhedron represents
one Mg2+ ion. (b) A cage A from one framework positioned in cage B from another one and interactions (yellow dashed line) between them.
Fig. 4. Views of the coordination environments of Mg1 and Mg2 ions and Mg6O3 cluster in
2. Hydrogen atoms have been omitted for clarity. Symmetry operation: c = x, y + 2, z;
d = x + 1, y + 2, z; e = x + 1, y, z.
44
Fig. 5. Views of (a) cage A and (b) cage B constructed by Mg6 units and BTB linkers in 2. (c) The mutual connection of eight cage As and the formation of a cage B, which exhibits one
framework in 2. The large pale blue sphere represents the space inside cage A. Color scheme as follows: Mg (green spheres), O (red spheres), C (gray spheres), the stick model of BTB
(blue and gray).
Acknowledgments
We would like to thank Prof. Junfeng Bai (Nanjing University, China)
for his guidance in the whole research and the members in his laboratory for their help in the experimental work.
Appendix A. Supplementary material
Crystallographic data for the structure analysis have been deposited
with the Cambridge Crystallographic Data Centre, CCDC Nos. 1016683
(1) and 1016684 (2). These data can be obtained free of charge from
the Cambridge Crystallographic Data Centre via http://www.ccdc.ac.
uk/data_request/cif. Supplementary material associated with this article
can be found, in the online version, at http://dx.doi.org/10.1016/j.
inoche.2014.12.012.
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