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A zeolite supramolecular framework with LTA

topology based on a tetrahedral metal–organic
Cite this: DOI: 10.1039/c8cc08965e
cage†
Received 11th November 2018,
Accepted 21st December 2018 Hai-Xia Zhang,‡a Xiaodong Yan, ‡a Yu-Xin Chen,a Shu-Heng Zhang,a Tao Li,a
Wang-Kang Han,a Ling-Yu Bao,a Rui Shena and Zhi-Guo Gu *ab
DOI: 10.1039/c8cc08965e

rsc.li/chemcomm

An unprecedented zeolite supramolecular framework featuring

truncated cuboctahedral and truncated octahedral cavities was
self-assembled from tetrahedral metal–organic cationic cages
and tetrahedral anions. This crystalline porous material could trap
iodine and organic dye molecules, and its solid state spin-crossover
behavior was affected by guest encapsulation.

Aluminosilicate Linde type A (LTA) zeolite is an industrially

important porous zeolite that is extensively used for adsorption
and separation processes, and as catalytic materials for petroleum
refining, and ion exchange materials for water softening and
effluent treatment.1 The LTA framework with cubic symmetry is
formed by two types of cages, truncated cuboctahedra (a-cage) and
truncated octahedra (b-cage), which are linked by double 4-rings.2
This unique LTA topology has been established for inorganic
zeolites composed of TO4 tetrahedrons bridged by m2-O atoms
with a T–O–T angle of ca. 1451 (Fig. 1a), and zeolitic imidazolate
frameworks (ZIFs) composed of Zn(Im)4 tetrahedrons and m2-Im
linkers with a Zn–Im–Zn angle also of 1451 (Fig. 1b).3 Recently,
supramolecular hydrogen-bond interactions between special
organic molecules have been proved to be an effective strategy to
obtain an LTA structure, in which the configuration and geometry
of the building blocks play a decisive structure-directing role.4
However, there are great challenges in assembling a zeolite supra-
molecular framework with LTA topology by using coordination
compounds as building blocks.
Metal–organic cages are discrete, highly symmetric molecular
cage compounds constructed by coordination bonds of inorganic
a
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education,
School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122,
P. R. China. E-mail: zhiguogu@jiangnan.edu.cn
b
International Joint Research Center for Photoresponsive Molecules and Materials,
School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122,
P. R. China
† Electronic supplementary information (ESI) available: Experimental details, general
characterization, additional plot and discussion. CCDC 1873319. For ESI and crystallo-
graphic data in CIF or other electronic format see DOI: 10.1039/c8cc08965e
‡ These authors contributed equally.
Fig. 1 The building units of the zeolite structure: (a) silica tetrahedron (Si:
pale blue; O: red); (b) the ZIFs (C: grey; N: blue; Zn: turquoise); (c) tetrahedral
metal–organic M4 cage and tetrahedral anion X formed XM4 and MX4
tetrahedrons (M: purple; X: green).
metal ions and organic ligands.5 The regular polyhedral geometry,
tunable cavity size, adjustable ligands, alterable counterions, and
optional metal centres of metal–organic cages make them ideal
building blocks for constructing supramolecular frameworks.
However, assembling metal–organic cages into a well-organized
architecture especially a zeolite supramolecular framework is still
challenging likely due to the uncontrollable and non-directional
intermolecular interactions.6 Based on inorganic zeolites and
ZIFs, a tetrahedral building unit is an essential prerequisite for
constructing a zeolite framework.7 Therefore, tetrahedral cationic
metal–organic cages with tetrahedral anions inherently possess
fundamental building elements of a zeolite supramolecular
framework (Fig. 1c). Under the right circumstances, the positive
charge centre of the metal ions (M) in tetrahedral metal–organic
cages and the negative charge centre of the anions (X) may form
MX4 and XM4 artificial tetrahedrons through electrostatic
interaction, and it is expected to form a zeolite supramolecular
framework.
Herein, we report a tetrahedral iron(II) metal–organic cage,
which is further assembled with tetrahedral ClO4 anions to form
a rare LTA topological supramolecular framework. The high

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porosity of this supramolecular framework was confirmed by
adsorption of iodine and dye molecules. The effect of guest on
the spin-crossover properties of the supramolecular framework
was investigated.
1 was synthesized by self-assembly of 3,5-di(2-(1-(imidazole-
2-carboxaldehyde))methyl)toluene, iron(II) perchlorate hydrate
and 1-phenylethylamine in acetonitrile solution (see the ESI†).
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and coordination (Fe - N) bonds were formed during the one-
pot self-assembly process.8 The IR spectrum of 1 shows typical
absorptions for the stretching of the imidazole-imine (CQN)
groups at 1607 and 1571 cm 1. The peaks at about 1097 cm 1
reveal the existence of ClO4 (Fig. S5, ESI†). The 1H NMR
spectrum of 1 shows signals from two imidazole protons
at 10.65 and 10.87 ppm, and the CQN protons at 14.08 ppm

Dark purple crystals were obtained in a few days by slow vapor (Fig. S6, ESI†). The high resolution mass spectra (HRMS) of 1
diffusion of diethyl ether into the reaction mixtures. reveal molecular ion peaks at m/z 1269.58 and 1954.09 corres-
The crystals of 1 remained stable in air and common solvents, ponding to [1(ClO4)5]3+ and [1(ClO4)6]2+ (Fig. S7, ESI†). 1 is
such as n-hexane and water (Fig. S4, ESI†). The covalent (CQN) stable at temperatures up to 195 1C as shown by TGA analysis

Fig. 2 Illustration of the X-ray crystal structures of 1. (a) Iron(II) tetrahedral cage (ORTEP, 20% ellipsoids). All H atoms and anions have been removed for
clarity; C: grey; N: blue; and Fe: purple. The green broken lines connect four vertices of the Fe4 tetrahedron. (b) One edge of the Fe4 tetrahedron and one
vertex of the Fe4 tetrahedron. (c) The two neighboring cages are linked by electrostatic interactions (indicated by the turquoise lines; O: red; and Cl:
green). (d) Artificial double 4-rings formed by a metal–organic cage with four anions situated on the windows of the Fe4 tetrahedron. (e) Artificial
truncated octahedron (b-cage) formed through assembling twelve iron(II) centers with twelve ClO4 anions. (f) The double 4-rings is connected with two
b-cages. (g) Artificial truncated cuboctahedra (a-cage) formed through assembling twenty four iron(II) centers with twenty four ClO4 anions. (h) Each
a-cage is surrounded by twelve double 4-rings. (i) Supramolecular LTA topology, only Fe atoms and Cl atoms are retained for clarity.

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(Fig. S8, ESI†). The phase purity of 1 was checked by powder
X-ray diffraction (PXRD) (Fig. S9 and S10, ESI†).
Single-crystal X-ray diffraction analysis reveals that 1 crystal-
lized in the cubic F23 space groups with a giant unit cell volume
of 157931(18) Å3 (Table S1, ESI†). In each tetrahedral cage of 1
(Fig. 2a), four Fe(II) ions occupy the vertices of the tetrahedron
and six C2-symmetry ligands define the edges with an average
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Fe


Fe separation along the edges of 9.59 Å. Each iron(II)
center coordinates with three ligands forming a distorted
FeN6 octahedral geometry, while each ligand connects two
iron(II) centers (Fig. 2b). The average Fe–N bond length is
1.98 Å, indicating the low-spin state of the Fe(II) center.9 Rich
intramolecular p–p interactions exist between each imidazole
and phenyl ring of the adjacent ligand with a center–center
distance ranging from 3.552 to 3.690 Å (Fig. S11, ESI†). The
tetrahedral cages in 1 pack in window to vertex stacks and the
anions are decorated around the vertexes or the windows of
the Fe4 tetrahedron. Each ClO4 ion is surrounded by two
tetrahedral cages in the crystal lattice, and the positive Fe4
cages and the negative ClO4 ions are connected through the
electrostatic interactions (Fig. 2c). In addition, the anions also
act as hydrogen bond donors forming C–H


O hydrogen bonds
with the protons of methyl and phenyl (Fig. S12, ESI†).
It is interesting that these isolated tetrahedral iron(II) metal–
organic cages and tetrahedral ClO4 anions are further assembled
into a higher-order supramolecular framework. One Fe4 cage and
four adjacent anions form a cube or double 4-rings with four Fe
atoms and four Cl atoms alternately occupying the vertexes
(Fig. 2d). By linking the Fe atoms and Cl atoms, artificial truncated
octahedrons (b-cages) containing six quadrangles and eight
hexagons can be obtained (Fig. 2e). It should be noted that
the single crystal morphology of 1 is also truncated octahedron,
which is strikingly similar to the internal molecular structure
of the b-cages (Fig. S13, ESI†). Each b-cage is connected with
six adjacent b-cages through double 4-ring units (Fig. 2f). In
addition, larger artificial truncated cuboctahedrons (a-cages)
containing twelve quadrangles, eight hexagons and six octagons
are formed (Fig. 2g). The shortest Fe


Fe and Cl


Cl distances
in 1 are about 12.97 and 11.52 Å, which generate large pores
with a diameter of 17.99 and 28.90 Å for the b-cage and a-cage,
respectively. One a-cage is in contact with twelve double 4-rings
(Fig. 2h). In this way, a zeolite supramolecular framework with
LTA topology is finally constructed in the form of a simple cubic
arrangement of the b-cages connected by the double 4-rings,
and producing an a-cage in the center of the cell (Fig. 2i). This is
the first example of an LTA structure using metal–organic cages
as building blocks.
In order to confirm the porous structure of 1, the iodine
capture capacity was examined in solution and in vapor. By
soaking the crystalline samples of 1 in an iodine/n-hexane
solution at room temperature, the purple solution gradually
faded until completely colorless (Fig. 3a). The iodine concentration
continuously decreased over time to nearly zero, corresponding to
a removal capacity of 20.12 wt% (Fig. S15, ESI†). An iodine capture
experiment in vapor was also carried out by exposing 1 to iodine
vapor at 75 1C. Upon standing, the mass of 1 was found to increase
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Fig. 3 (a) Time-dependent UV-vis absorption spectra of the iodine/n-hexane
solution (2 mmol L 1, 8 mL) upon addition of 1 (10 mg). (b) Gravimetric uptake
of iodine as a function of time at 75 1C. (c) Time-dependent UV-vis absorption
spectra of the Amaranth aqueous solution (AM, 5 mL, [AM] = 60 mmol L 1) upon
addition of 1 (15 mg). (d) Time-dependent UV-vis absorption spectra of the
Congo Red aqueous solution (CR, 5 mL, [CR] = 120 mmol L 1) upon addition of
1 (15 mg). The photographs of the bottles (insets) show the color of the iodine
and dye molecules before and after inclusion.
gradually by weighing, and an iodine uptake of 281 wt% was
determined, corresponding to 42.5 I2 per formula unit of 1
(Fig. 3b). This is consistent with a theoretical void space of
37.9% calculated from the crystal structure of 1 by PLATON.
The iodine vapor uptake capacity is higher than those of the
previously reported solid porous adsorbents, including metal
organic frameworks (MOFs),10 amorphous porous organic poly-
mers (POPs),11 and zeolites.12 The dye adsorption capacity of 1
was also investigated. The time-dependent UV-vis spectra
clearly showed a continuous decrease of the absorbance in
anionic dyes Amaranth (AM) and Congo Red (CR) (Fig. 3c and
d), and the color of the aqueous solution gradually became
lighter and almost colorless after 60 h. The AM and CR removal
capacity of 1 was 11.06 and 21.26 mg g 1, respectively (Fig. S17,
ESI†). The neutral dye neutral red (NR) and the cationic dye
methylene blue (MB) could hardly be adsorbed in the cavities of
1 (Fig. S18, ESI†). These results show that the LTA topology
structure of 1 with various cavities, such as double 4-rings,
b-cages and a-cages, was capable of capturing small iodine
molecules and large cationic dye molecules.
The structure of 1 contains iron(II) centers with an N6
coordination environment, which have two electron configurations,
t42ge2g (high-spin HS) and t62ge0g (low-spin LS). Therefore, its magnetic
susceptibility was measured in the temperature range of 2–400 K. As
shown in Fig. 4a, 1 exhibits a gradual and incomplete spin-crossover
behavior. Upon increasing the temperature, the wMT value gradually
increased to ca. 3.92 cm3 k mol 1 at 200 K. As the temperature
increased to 400 K, the wMT value reached 11.20 cm3 k mol 1,
indicating that the four iron(II) centers are almost in the HS
state. And the thermal spin transition temperature T1/2 was
estimated to be 321 K. In contrast, after loading the guest
molecules, 1@I2 (Fig. 4b), 1@AM (Fig. 4c) and 1@CR (Fig. 4d)
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Fig. 4 Plots of wMT versus T for (a) 1, (b) 1@I2, (c) 1@AM, and (d) 1@CR.
displayed paramagnetic behaviors with no SCO properties. This
phenomenon can also be confirmed by IR spectroscopy, Raman
spectroscopy and solid UV-vis spectroscopy13 (Fig. S19–S21,
ESI†). The disappearance of the SCO behaviors of 1@I2,
1@AM and 1@CR could be attributed to the following reasons:
(I) the donor–acceptor interactions between the electron-rich
Fe(II) framework and the electron-deficient iodine molecules;
(II) the electrostatic interactions between the cationic frame-
work and the anionic dye molecules; and (III) the intermolecular
interactions (such as hydrogen-bond interactions, p–p interactions,
and CH


p interactions) between the abundant phenyl groups
on the cages and the dye molecules. This is in accordance
with other reported porous SCO compounds, in which the
guest such as benzene or iodine molecules caused T1/2 to
move to low temperature and even made the SCO properties
disappear.14
In conclusion, we have presented the construction of a
tetrahedral metal–organic cage that is able to self-assemble
into a rare supermolecular zeolite framework with LTA topology.
Such supermolecular zeolite frameworks possess much larger
a-cage and b-cage cavities compared to traditional inorganic
zeolites and ZIFs, thereby showing good ability to adsorb large
size guest molecules. We believe that this new approach will
initiate the search for other supermolecular zeolite frameworks
with metal–organic polyhedral compounds as building blocks.
Simultaneously, the fascinating optical, electrical, magnetic,
and catalytic functions of metal–organic cages can be introduced
into the supermolecular porous framework to realize multi-
functional metal–organic materials.
This work was supported by the National Natural Science
Foundation of China (21771089), the Fundamental Research
Funds for the Central Universities (JUSRP51725B, JUSRP51513),
the project for Jiangsu Scientific and Technological Innovation
Team, and the MOE & SAFEA for the 111 Project (B13025).
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Conflicts of interest
There are no conflicts to declare.
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