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Inorganic Chemistry Communications 52 (2015) 4145

Contents lists available at ScienceDirect

Inorganic Chemistry Communications


journal homepage: www.elsevier.com/locate/inoche

Solvent-induced generation of two magnesium-based metalorganic


frameworks with doubly inter-penetrated ReO3 nets constructed from
the same linkers but distinct inorganic nodes
Congyu Zuo a,, Zhiyong Lu b, Mingxing Zhang b
a
b

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.

Porous metalorganic frameworks (MOFs) have been extensively


researched for nearly two decades due to their intriguing topologies
[1] and promising applications in the elds of gas storage [24],
molecule separation [58], catalysis [9,10], etc. MOFs are generally
synthesized by the coordination of metal ions or metal ion clusters to
organic ligands in proper solvent system [11]. Compared with other
porous materials (e.g., zeolites and porous carbon materials), MOFs
have their competitive advantages that the structures can be tailored
or tuned more easily. For structure diversication and property
optimization, most contributions were focused on the deliberate design
of organic ligands [1214]. However, metal centers, used as connection
nodes, have an effect on the architectures and performances of MOFs as
well as ligands and the researches in this regard are relatively few so far.
In the only reports, the studies are almost conned to the decoration of
metal center, the substitution of different metal ions, or the usage of
metalorganic polyhedra in MOFs [1517]. If the nodes are replaced
but the metal ions, used for constructing them, keep unchanged, and
meanwhile the framework structures of complexes remain the same,
it may provide a new way for exploring the factors that inuence
MOFs' properties because only the structures of nodes are different
among them.
For attaining the objective above, what has rstly to be done is the
preparation of such a kind of MOF. In this work, a rigid tricarboxylate
ligand, 4,4,4-benzene-1,3,5-triyl-tribenzoate (noted BTB), and a light
Corresponding author.
E-mail address: cyzuo@aust.edu.cn (C. Zuo).

http://dx.doi.org/10.1016/j.inoche.2014.12.012
1387-7003/ 2014 Elsevier B.V. All rights reserved.

metal ion, Mg2 +, were intentionally selected to construct them. BTB


linker, an augmented benzene derivative of the trimesate species, has
a moderate size and enough rigidity, which would afford a space for
forming bulky metal ion clusters [1820]. The usage of Mg2+ is based
on the fact that its radius is similar to those of transition metal ions
such as Zn2+ and Cu2+ but its density is lower than them, which can
facilitate the preparation of MOF-type materials with a reduced
framework density [18,21,22]. Afterwards, the reaction conditions
have been explored and then two magnesium-based MOFs,
(NH2Me2 ) 2[Mg(BTB) 4/3 (H2 O)2 ]7DMF4H2 O (1) and (NH 2Me2 ) 2
[Mg 6O 3 (BTB) 8/3 (H2 O) 4 ]15DMSO5H2 O (2), were successfully
synthesized (DMF = N,N-dimethylformamide, DMSO = dimethyl
sulfoxide). Their structures exhibit the same frameworks and shape of
pores, but comprise different Mg-containing nodes.
Complex 1 was prepared by heating Mg(NO3)26H2O and H3BTB in
DMF/H2O (5:0.7 v/v) at 120 C for 48 h. It appeared in the form of
light yellow cube-shaped crystals and was insoluble in common organic
solvents such as DMF, ethanol, chloroform, acetone, 1,4-dioxane, and
diethyl ether. Complex 2 was synthesized in the solvent of DMSO/
DMF/H2O (5:1.5:1 v/v). The remaining reaction conditions for generating 2 are the same as those for 1. 2 also emerged as light yellow cubeshaped crystals and showed similar insolubility to 1. Their structures
were determined by single-crystal X-ray diffraction.
Complex 1 crystallizes in cubic space group Im3 [23], containing onequarter Mg2+ ion, one-third BTB3 ligand, half a [NH2(CH3)2]+ ion, and
two one-quarter coordinated water molecules in the crystallographically
independent unit (Fig. S1). In 1, each Mg2+ ion shows an octahedral

42

C. Zuo et al. / Inorganic Chemistry Communications 52 (2015) 4145

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.

coordination geometry by binding four carboxylate groups from four


BTB3 ligands at the equatorial positions (MgOBTB = 2.0547(11) )
and two water molecules at the axial positions (MgOW = 2.064(2)
2.129(2) ) (Fig. 1), and each carboxyl group from the BTB linker
connects one Mg2+ ion in a monodentate mode (Fig. S2), which gives
rise to the formation of a (4,3)-connected 3-D network (Fig. S3).
In this framework, two identical Mg2 + ions being 9.418 apart
could be viewed as a dinuclear unit. These units are arranged in such a
way that they occupy each corner of a super-octahedral polyhedron
and then constitute a cage (named cage A) with tritopic BTB spacers
being located on each triangular face of the octahedron (Fig. 2a). The estimated distances are 2.005 nm from face to face and 2.735 nm between

two opposite corners of the cavities. Such super-octahedral blocks are


stacked to each other by sharing all their Mg2 units along a, b and c
axes, which leads to the formation of a 3-D network corresponding to
the primitive cell of the ReO3 type (Fig. 2c) [1820]. The network is similar to the structure of MIL-123 reported by G. Frey and his co-workers
[18], but the prototypes of their inorganic nodes are obviously quite
different. Owing to the augmentation of the vertexes of the superoctahedron, eight adjoining cages, located at the vertexes of a cube,
enclose a bigger cavity (named cage B) [17,24]. It is also composed
of eight BTB3 and twelve Mg2 + ions, but has six larger windows
(2.735 1.793 nm2) compared with cage A (Fig. 2b). Cage As and Bs
are embedded in each other and stack up in the same way, which results
in a 3-D framework with very high porosity.
It may be such space in this framework that can allow another
identical framework to penetrate into the former to reinforce their
structure stabilities (Fig. 3a). In the schematic structure, the icosahedra
come from the simplication of cage A where Mg2+ ions are viewed as
vertexes of the polyhedron. In this double-interpenetrated structure, a
cage A from one framework locates in a cage B from the other (Fig. 3a,
b). Between the two frameworks, a slight gap exists. Here, two neighboring triangle faces, constructed by two BTB linkers from different
frameworks, are parallel and stack each other up with a rotation angle
of 60 [1820], through interactions between the central benzene
rings of the two BTB spacers (CC = 3.632 ) (Fig. 3b, S4). Although
the structure of 1 is two-fold interpenetrated, its solvent accessible
volume calculated using the PLATON is 46.7% [25], and the estimation
is done under the condition that coordinated water molecules and
dimethylamine cations have not been removed.
Complex 2 also crystallizes in the Im3 space group [26], but its
crystallographically asymmetric unit is different from the one of
complex 1, which consists of one-third BTB3 ligand, one-quarter
Mg1 cation, half a Mg2 cation, one-quarter [NH2(CH3)2]+ ion, two
one-quarter of coordinated water molecules, one-quarter 3-O atom
and one-eighth 4-O atom (Fig. S5).
Their identical space groups result from the same symmetry of their
frameworks, while their different asymmetric units lead to their distinct
nodes which constitute indispensable parts of the frameworks. The
nodes stem from a hexanuclear cluster Mg6 in 2 instead of the dinuclear
unit Mg2 in 1. It is a novel MgO cluster, containing two Mg1 and four
Mg2 cations, one 4-O and two 3-O atoms, and two bridging and two
terminal water molecules (Fig. 4). Noticeably, these atoms, except
hydrogen atoms from water molecules, are all in a plane. Herein, two
Mg1 atoms are distributed symmetrically at two terminal ends of the
motif. Each Mg1 is six-coordinated with an octahedron geometry

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).

C. Zuo et al. / Inorganic Chemistry Communications 52 (2015) 4145

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.

constructed by four oxygen atoms of carboxylate groups from four BTB


ligands at equatorial vertexes, one terminal water molecule (O1W) and
one 3-O atom (O3) at polar vertexes, respectively (Mg1O =
2.0511(13)2.077(3) ). Four Mg2 atoms are arranged in a rectangular
formation (3.148 2.936 2) which is positioned in the intermediate
section of the hexameric block. They are all linked to a centered 4-O
atom (O4) and meanwhile each Mg2 atom pair is bridged by one
water molecule (O2W) along the long axis of the cluster. Each Mg2 is
rarely ve-coordinated with distorted hexahedron geometry which
vertexes are composed of two bridging carboxylate O atoms, one bridging water molecule (O2W), one 3-O atom and one 4-O atom. The
range of Mg2O bond distance is 1.7664(17)2.1523(9) , where the
Mg2O3 distances of 1.7664(17) are even shorter than those of
1.773 reported by J.-C. Berthet et al. [27]. Two Mg2 atoms and one
Mg1 atom, located at one terminal of the cluster, are disposed in a triangle formation. The three Mg atoms are connected together by a 3-O
atom.
The Mg1 and its adjacent Mg2 atom are bridged again by two
dimonodentate carboxylate groups from two BTB linkers, so a whole
Mg6O3 cluster is linked to eight BTB ligands. As each carboxyl group
adopts a dimonodentate bridging mode, a BTB ligand is coordinated to
three Mg6 hexamers. If the hexanuclear units are viewed as the same
connection nodes as Mg2 units in 1, a similar framework to that of 1
will be formed and similar cages A and B to those in 1 will be presented
(Figs. 5, 6a). On the basis of the above, tritopic linkers are further
simplied to three-connected nodes, and then the structure of 2 can
be topologically recognized as a (8,3)-connected the-type net with the
Schli symbol of {43}8{48.64.812.104}3 (Fig. S6).
Compared with the corresponding sizes in 1, the distances from face
to face (2.000 nm) and between the two opposite vertexes (2.726 nm)
of cage A in 2 are all slightly shorter, which would be attributed also to
the slightly shorter distance (9.237 ) between two Mg1 ions in the
hexanuclear cluster. Intriguingly, the distance between two parallel
central benzene rings of the BTB spacers from two different frameworks
(3.605 ) is also slightly shorter than that in 1 (Figs. 6b, S7). However,
the analogous free void volume of 54.2% in 2, as estimated by PLATON
[25], is larger than that in 1, which should be ascribed to the ratio of
the dimethylamine cation to cage A in 2 being half the one in 1.
Besides small differences in their structures, there are many similarities between them. Their estimated pore sizes are about 1.8 nm from
face to face and 2.6 nm between two opposite corners of the superoctahedral cavities, which is evidenced by a large amount of DMF or
DMSO and water species residing in their cages. Thermogravimetric
analyses (Fig. S8) along with elemental analyses indicate that about
free 14 DMF and 8 water molecules per Mg2 unit in 1 and 15 DMF and
5 water molecules per Mg6O3 unit in 2 exist in their over-all frameworks. IR spectrum for 1 (Fig. S9) displays a specic strong vibration

band corresponding to a C_O frequency at 1663 cm1 from the DMF


species. An intense absorption band at 1018 cm1 in the IR spectrum
for 2 (Fig. S10) can be assigned to the asymmetric stretch of S_O
bond, the red-shift of which is probably involved in the formation of hydrogen bonds between DMSO and water molecules [28]. Additionally,
their apparent solvent accessible spaces are estimated to be around
50% from the PLATON calculations.
Obviously, the main difference between 1 and 2 is shown in the
inorganic building blocks. The reason for the difference only lies in
their solvent system. In the process of synthesizing 1, DMF serves as
the main component of the solvent and water is accessorial. With
water increasingly added, the crystals containing hexamers do not
occur, but a polymeric magnesium formate is obtained instead. When
solvent composition is changed and DMSO becomes the main component together with a suitable amount of DMF and water, however, the

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.

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C. Zuo et al. / Inorganic Chemistry Communications 52 (2015) 4145

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).

crystals containing Mg6O3 clusters of 2 emerge. The phenomena above


indicate that DMSO should be the key factor to form the Mg6O3 cluster.
Indeed, water and DMF are also indispensable because any crystals
would not be generated without them in this experiment. Water is
the major source of some segments of the cluster, while DMF can
provide dimethylamine that facilitates the deprotonation of H3BTB.
DMSO is favorable to the formation of metal cluster that has also
been exemplied in some other literatures [19,20]. Besides, DMSO
might act as a template reagent during the construction of the
super-octahedral cage in 2, and DMF might play the similar role for
1 [29].
In summary, only by changing the composition of the solvent
system, two magnesium-based MOF-type compounds, 1 and 2,
have been synthesized. Their structures are built up from similar
large super-octahedral cages, which connect to each other to
generate two-fold interpenetrated ReO3 nets. Using DMF as solvent
in company with a little water, a dinuclear unit Mg2 in 1 is formed,
which consists of two independent Mg centers. When DMSO acts as
the main component of the solvent together with an appropriate
amount of DMF and water used, a new hexanuclear block Mg6O3 in
2 is obtained, which implies that DMSO favors the formation of the
metal cluster. That the frameworks of 1 and 2 are still kept alike is
probably related to the template reagent roles of DMF and DMSO
used.

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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C. Zuo et al. / Inorganic Chemistry Communications 52 (2015) 4145

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