A 4 + 4 strategy for synthesis of zeolitic metal-organic frameworks: An indium-MOF with SOD topology as a light-harvesting antenna

Article abstract of DOI:10.1039/c3cc43383h

A zeolitic metal-organic framework with a SOD topology, (Et ₂NH₂)[In(BCBAIP)]·4DEF·4EtOH (H ₄BCBAIP: 5-(bis(4-carboxybenzyl)amino)isophthalic acid) (1), has been constructed by a 4 + 4 synthetic strategy from tetrahedral organic building units and In³⁺ ions. Compound 1 could adsorb organic dyes and be used as a light-harvesting antenna.

Full text of DOI:10.1039/c3cc43383h

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A 4 + 4 strategy for synthesis of zeolitic metal–organic
frameworks: an indium-MOF with SOD topology as a
light-harvesting antenna†
Cite this: DOI: 10.1039/c3cc43383h
Received 7th May 2013,
Accepted 11th June 2013
a
b
a
a
a
Libo Sun, Hongzhu Xing, Zhiqiang Liang,* Jihong Yu* and Ruren Xu
DOI: 10.1039/c3cc43383h
www.rsc.org/chemcomm
A zeolitic metal–organic framework with a SOD topology, (Et
In(BCBAIP)]ꢀ4DEFꢀ4EtOH (H BCBAIP: 5-(bis(4-carboxybenzyl)amino)- nodes through direct coordination interaction. For using such a 4 +
isophthalic acid) (1), has been constructed by a 4 + 4 synthetic strategy 4 strategy, it is necessary to design and synthesize organic ligands as
2 2
NH )- prepared by the connection of inorganic and organic tetrahedral
[
4
3+
from tetrahedral organic building units and In ions. Compound 1 tetrahedral nodes in the final crystal structure. So far only two
could adsorb organic dyes and be used as a light-harvesting antenna. isostructural ZMOFs have been reported that have four-connected
+
+
4f
boron imidazolate complexes and four-connected Li or Cu ions.
Recently, we have focused on the design and synthesis of novel
Zeolites are a class of porous crystalline materials with excellent
thermal and chemical stable properties, and are widely used in ligands based on isophthalic acid, which were used to construct
13
industrial applications, such as catalysis, ion exchange and adsorp- MOFs with interesting properties. In this work, a tetracarboxylate
1
tion. A fundamental strategy for the construction of traditional ligand 5-(bis(4-carboxybenzyl)amino)isophthalic acid (H BCBAIP)
4
zeolitic materials is based on the rational selection of four- was designed and synthesized as the four-connected tetrahedral
4
+
4+
3+
4+
2+
4
connected tetrahedral nodes (TO , T = Si , Ge , Al , Ga , Be , linker. In the ligand, the centered N atom plays a crucial role in
3+
2+
2
2ꢁ
B , Zn etc.) with right T–O–T angles, where the O anion can act the conformation, and the ligand can be considered as an organic
as a bridging atom. Up to now, 206 kinds of zeolitic topologies have tetrahedral node with four carboxylate groups as the vertices of the
3
been identified. In recent decades, zeolitic metal–organic frame- tetrahedron. It is well known that metal ions show different coordi-
4
works (ZMOFs) have attracted increasing interest due to their nation ability and could be simplified as various inorganic topolo-
5
6
7
3+
potential applications in catalysis, gas storage and separation.
gical nodes in the MOF structures. Notably, the In ion shows great
As one kind of porous material different from zeolites, the con- facility to coordinate to four carboxylate groups to form a tetrahedral
1
4
struction of MOFs can be divided into two parts: the choosing of four-connected {In(O C) } group, which was also reported in the
2
4
8
12
organic ligands and the selection of metal ions. In order to ZMOFs obtained by using the 4 + 2 synthetic strategy. With above
construct ZMOFs, the 4 + 2 synthetic strategy, which is very popular considerations, we have successfully synthesized a zeolitic metal–
9,10
and widely used up to now, is employed.
2 2
In fact, with judicious organic framework compound with SOD topology, (Et NH )-
selection of metals and ligands, most types of ZMOFs were synthe- [In(BCBAIP)]ꢀ4DEFꢀ4EtOH (1) by using this 4 + 4 strategy. Compound
sized based on the mimicking of the Si–O–Si angle of approximately 1 exhibits dye-adsorption and light-harvesting properties.
1
0
1
451 by T–L–T angles through the 4 + 2 strategy. This strategy has
1 was synthesized by a solvothermal reaction of InCl ꢀ6H O and
3
2
led to the imidazolate type ZIFs and heterocyclic carboxylate H BCBAIP in a mixture of N,N-diethylformamide (DEF) and
4
10,11
ZMOFs.
In addition, Zheng et al. utilized the bent carboxylate C H OH at 95 1C. Light brown block shaped crystals were obtained
2 5
ligand instead of the heterocyclic ligand to generate a suitable after 72 h. The crystal structure of 1 was determined using single-
12
T–L–T angle and successfully synthesized a series of ZMOFs. On crystal X-ray diffraction.‡ The purity of the samples was proven by
the other hand, it is not surprising that ZMOF materials can be the powder X-ray diffraction pattern, which matches well with the
simulated one (Fig. S9, ESI†).
a
The structure analysis reveals that 1 crystallizes in the hexagonal
R3%c space group. The detailed coordination environment is depicted
State Key Lab of Inorganic Synthesis and Preparative Chemistry, Jilin University,
Changchun, 130012, China. E-mail: liangzq@jlu.edu.cn, jihong@jlu.edu.cn;
Fax: +86-431-85168608; Tel: +86-431-85168608
in Fig. S1 (ESI†). In each asymmetric unit, there exists half one
b
3+
4ꢁ
College of Chemistry, Northeast Normal University, Changchun, China
Electronic supplementary information (ESI) available: Experimental details, IR,
independent In ion, half one organic BCBAIP anion, and the
†
+
negative charge of the framework is balanced by half one Et
2 2
NH
TGA, UV-vis, luminescence, dyes adsorption, gas sorption, fluorescence decay,
cation, which was generated from the decomposed DEF. Both of the
crystallographical data, selected bond lengths and angles for compound 1. CCDC
3
+
4ꢁ
In ion and the centered N atom of the BCBAIP ligand are
9
18529. For ESI and crystallographic data in CIF or other electronic format see
3+
DOI: 10.1039/c3cc43383h
located on the crystallographically-imposed 2-fold axis. Each In
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4
ꢁ
Fig. 2 (a) The In(O
2
C)
4
unit as the T
1
node; (b) the BCBAIP anion as the T
2
node; (c) the sodalite cage of compound 1.
Fig. 1 The structure analogy between aluminosilicate zeolite sodalite and
compound 1.
0
4ꢁ
BCBAIP
the {In(O
anion are 1161 and 801 (Fig. S6, ESI†). The linkage of
0
4ꢁ
2
C) } group and BCBAIP results in a 2D In-MOF with sql
4
ion is bonded to four carboxylates to form a four-connected topology. The failure in the formation of ZMOFs can be ascribed to
0
{
In(O
linker to bridge four In ions. Assuming the In ions and the
ligand as four-connected nodes, the TOPOS analysis of this network carbon dioxide (at 273 K) adsorption experiments were performed by
2
C)
4
} group, while each ligand serves as a four-connected the unsuitable angles in the H
4
BCBAIP ligand.
3+
3+
To evaluate the porosity of compound 1, nitrogen (at 77 K) and
2
4
results in a zeolitic SOD topology with a point symbol of (4 ꢀ6 ) using the samples activated at 85 1C (Fig. S9b, ESI†). Unfortunately,
Fig. 1). The void volume of 1 calculated using PLATON/SQUEEZE is the Brunauer–Emmett–Teller (BET) surface area is rather low
2
cations (209 m g , Fig. S10, ESI†), and this may be caused by the cationic
2 2
NH blocked in the cages. The CO uptake of 1 at 273 K and
work viewed along the [001] direction and shows two kinds of 722 mmHg is 37.6 cm g . In order to testify the accessibility of the
(
7
+
2
ꢁ1
5.2% of the unit cell volume upon removal of the Et
2
NH
15
+
and guest solvent molecules. Fig. S2 (ESI†) illustrates the frame- Et
2
3
ꢁ1
windows. The hexagonal window is constructed by three ligands porosity of 1, the dye-adsorptions were measured using a range of
1
6
and three {In(O
2
C)
4
} units with a size of ca. 14 ꢂ 14 Å. The relatively different dyes. When immersed into the methanol solutions of
smaller rectangle window (ca. 7.5 ꢂ 10.5 Å) is formed by two ligand Methylene Blue (MB), Rhodamine B (RB), Rhodamine 6G (R6G),
molecules and two {In(O C) } units. The sodalite cage formed in the Coumarin 343 (C343) and Coumarin 6 (C6) for 6 h at room tem-
2
4
framework has a size of ca. 26 ꢂ 26 ꢂ 8.2 Å.
Further insight into the structure of 1 explains the 4 + 4 strategy toward these dyes as monitored using UV-vis absorption spectroscopy
by the judicious selection of the H BCBAIP ligand and the indium (Fig. S11, ESI†), in the order of MB > RB > R6G > C343 E C6, which
ion. 1 is constructed by two kinds of different T nodes from the could be mainly ascribed to the anionic nature of the framework of 1.
perature, respectively, 1 presents different kinetic adsorption behavior
4
+
simplified form. One is from {In(O
2 4 1 2 2
C) } (T ) and the other is from The Et NH ions in the channels can be rapidly exchanged by
the ligand (T ) (Fig. 2a and b). The linkage of these two kinds of cationic MB, RB and R6G, while the neutral C343 and C6 are not the
2
T nodes forms a distorted SOD cage (Fig. 2c and Fig. S3, ESI†). The favored dyes for the exchange. Since the size of MB is smaller than
design of the H BCBAIP ligand with the T node and the suitable that of RB and R6G, it exhibits the most rapid adsorption rate.
4
T–O–T angles is the key for the 4 + 4 strategy. The crystal structure of
pure H BCBAIP reveals that the ligand adopts a tetrahedral configu- C343@1), as confirmed using the UV-vis absorption spectroscopy
ration in the structure (Fig. S4, ESI†), and the centered N atom could (Fig. 3 and 4), inspired us to further study their light-harvesting
The successful loading of C6 and C343 into 1 (C6@1 and
4
17
be seen as a T node. By mimicking the T–O–T angles in the zeolite properties. As shown in Fig. 3 and 4, the emission of 1 (donor) in
structures, the H BCBAIP ligand itself as the T node can supply the solid state overlap well with the absorption spectra of the two
4
suitable T–L–T angles (116–1241) for the construction of 1 (Fig. 2b). dyes (acceptor) in methanol, which favors the energy transfer
In order to further investigate the influence of T–L–T angles of the process. In the case of C6@1 and C343@1, when excited at
ligand on the formation of 1, we have designed another tetra- 381 nm in the solid state, the emission of the host framework is
carboxylate ligand 5-(bis(3-carboxybenzyl)amino)isophthalic acid quenched while the emissions of C6 and C343 dyes could be
0
(
H
4
BCBAIP ), which is similar to H
4
BCBAIP except for the position enhanced, respectively. These results indicate that the excitation
of carboxylate acid of the carboxybenzyl group. The solvothermal energy is transferred from the host framework to the guest dyes.
0
reaction of H
4
BCBAIP with indium salt only yielded a 2D In-MOF Compared with the lower emissions of dyes (dispersed in SiO
2
, ca.
(Fig. S5, ESI†). In this compound, the T–L–T angles of the 0.1 wt%, excited at 381 nm), the ordered porous structure of 1 for
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T = 296(2) K, F(000) = 11700, 69 588 reflections collected, 7969 indepen-
dent reflections (Rint = 0.0947) which were used in all the calculations.
1 2
After the refinement cycles, reliability factors were R = 0.0448, wR =
0
.0788 for [I > 2s(I)], and R = 0.1513, wR = 0.0878 for all 7969 data.
1
2
1
2
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C343@SiO (d, 0.1 wt%), C343@1 (e, 0.072 wt%,), lex = 381 nm. The inset
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2
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1
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4
compound possesses an anionic framework and a nano-sized
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3+
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1
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We thank the National Natural Science Foundation of China and
the State Basic Research Project of China (Grant: 2011CB808703) for
support of this work. H.X. thanks the Jilin Provincial Science and
Technology Development Foundation (201101007).
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Notes and references
‡
Crystal data for 1: C56
95 6
H N O16In, M = 1223.20, trigonal, space group
R3%c, a = 38.2369(10) Å, b = 38.2369(10) Å, c = 22.7356(12) Å,
3
ꢁ3
ꢁ1
V = 28787.4(19) Å , Z = 18, D
c
= 1.270 g cm , m = 0.436 mm
,
18 X. Zhang, Z.-K. Chen and K. P. Loh, J. Am. Chem. Soc., 2009, 131, 7210.
This journal is c The Royal Society of Chemistry 2013
Chem. Commun.