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Synthesis of homochiral zeolitic metal–organic

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frameworks with amino acid and tetrazolates for

Cite this: RSC Adv., 2017, 7, 4872
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chiral recognition†
Received 21st November 2016
Min-Yu Li, Fei Wang,* Zhi-Gang Gu and Jian Zhang*
Accepted 3rd January 2017
By mixing amino acids and tetrazolate ligands, a series of homochiral zeolitic metal–organic frameworks
DOI: 10.1039/c6ra27069g
(ZMOFs) with ABW topology have been synthesized, and these materials show permanent microporosity
www.rsc.org/advances and potential enantioselective recognition ability.

Introduction
Within the last few years, inorganic zeolites and zeolitic metal–
organic frameworks (ZMOFs) have received much attention due to
their fascinating tetrahedral structures, high stability, and
tailored functionalities.1–5 Among them, the combination of the
tetrahedrally coordinated divalent cations (M2+ ¼ Zn2+ or Co2+)
and uninegative azolate ligands (especially imidazolate and tet-
razolate derivatives) results in the successful development of
zeolitic imidazolate frameworks (ZIFs) and tetrahedral tetrazolate
frameworks (TTFs).4–7 TTFs7 possess uncoordinated N-heteroatom
sites from the m2-tetrazole ligands, and show promising potential
applications in carbon dioxide capture and separation.
As enantioselective separation of racemates is especially
important for the chemical and pharmaceutical industries,
homochiral MOFs with such a function have attracted a great Scheme 1 The synthesis strategy of the homochiral ZMOFs.
deal of attention in recent years.8,9 The most reliable approach to
prepare homochiral MOFs is to select a enantiopure ligand as the
primary linker to impart homochirality to the framework. The
In this work, we report a new approach to construct micro-
natural amino acids are ideal candidates because of their low cost
porous homochiral ZMOFs based on enantiopure amino acids
and strong coordination ability. So far, although tremendous
and tetrazolate derivatives. We select four enantiopure amino
efforts have been devoted to the design and synthesis of novel
acids (L-lanine (L-Ala)), D-lanine (D-Ala), L-serine (L-Ser), and (L-
homochiral MOFs based on optically pure amino acids and their
valine (L-Val)) in combination with 5-methyltetrazole (5-Hmtz)
derivatives,10,11 it remains highly challenging to construct
ligand (Scheme 1) to realize four homochiral ZMOFs Zn4(5-
homochiral MOFs with zeolitic topology. Recently, we have
mtz)6(L-Ala)2$2(DMF) (1L), Zn4(5-mtz)6(D-Ala)2$2(DMF) (1D),
developed one kind of homochiral ZMOFs based on enantiopure
Zn4(5-mtz)6(L-Ser)2$2(DMF) (2L) and Zn4(5-mtz)6(L-Val)2$2(DMF)
amino acids ligand.11 By choosing a pair of enantiopure amino
(3L) with ABW topology for the rst time. Furthermore, these
acids (L-Alanine and D-Alanine) as linkers and octahedral Ni(II)
materials show permanent microporosity and enantioselective
metal centers as 4-connected nodes, two homochiral MOFs with
recognition ability.
SOD topology are successfully synthesized. However, the short
Ni/Ni distance made it a dense framework without pore.
Experimental
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Measurements
Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R.
Elemental analyses of C, H and N were measured on a Vario
China. E-mail: wangfei04@irsm.ac.cn; zhj@irsm.ac.cn
† Electronic supplementary information (ESI) available: TGA, PXRD, and
MICRO E III elemental analyzer. The IR spectra (KBr pellets)
additional gures. CCDC 1511625–1511628. For ESI and crystallographic data in were recorded on a Magna 750 FT-IR spectrophotometer.
CIF or other electronic format see DOI: 10.1039/c6ra27069g Powder X-ray diffraction data were recorded on a Rigaku

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MultiFlex diffractometer with a scan speed of 5 min1. Results and discussion

Thermal stability studies were carried out on a NETSCHZ STA-
449C thermoanalyzer under N2 (room temperature-600  C Structural description
range) at a heating rate of 10  C min1. The gases adsorption Single crystal X-ray analysis revealed that four compounds are
isotherms were measured by using ASAP-2020 volumetric isostructural. Here, only the structure of 1L is described in
adsorption equipment. Circular dichroism (CD) experiments detail. 1L crystallizes in the monoclinic system with chiral space
were recorded with a Bio-logic MOS-450 CD Spectrometer at group P21. The asymmetric unit of 1L consists of four Zn(II) ions,
room temperature. six 5-mtz, two L-Ala anions and two ordered DMF molecules.
There are two kinds of Zn centers (Fig. 1a). One is tetrahedrally
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coordinated by three N atoms from three 5-mtz and one

Synthesis
carboxylate oxygen atom from L-Ala. The other one shows
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Colorless crystals of 1L were solvothermally synthesized by the a distorted trigonal bipyramidal conguration with ve-
self-assembly of Zn(NO3)2$6H2O, 5-Hmtz and L-alanine in DMF coordination, in which two N atoms from two 5-mtz and one
solvent. 1D, 2L and 3L were obtained by using D-alanine, L- amino N atom from L-Ala occupy the three equatorial, and two
serine, and L-valine respectively to replace the L-alanine under axial positions are occupied by one N atom from one 5-mtz and
the similar condition. The details of the synthesis of 1L, 1D, 2L one carboxylate oxygen atom from L-Ala. The Zn–O bond lengths
and 3L were described in the ESI.† range from 1.947 to 2.305 Å. The Zn–N bond lengths range from

Crystallography
Crystallographic data of 1L, 1D and 2L were collected on
a Mercury single crystal diffractometer equipped with graphite-
monochromatic Mo Ka radiation (l ¼ 0.71073 Å) at room
temperature. Crystallographic data of 3L was collected on
a SuperNova (Cu) single crystal diffractometer equipped with
graphite-monochromatic Cu Ka radiation (l ¼ 1.54184 Å) at
room temperature. The structures were solved by direct
methods and rened by full-matrix least-squares on F2. All the
structures were solved by using the program package SHELX-
2014/7.12 Non-hydrogen atoms were rened anisotropically, and
all hydrogen atoms bond C were generated geometrically.
Crystallographic data and structural renement details for 1L,
1D, 2L and 3L are listed in Table 1. The starting amino acids are
not optically pure, resulting in the high Flack values.13 CCDC Fig. 1 (a) The coordination environment of metal centers in 1L, 2L and
1511625 (1D), 1511626 (2L), 1511627 (1L) and 1511628 (3L) 3L; (b) the 3D framework of 1L with guest molecule DMF (ball and stick)
contain the ESI† crystallographic data for this paper. in the pores.

Table 1 Crystallographic data and structural refinement details for 1L, 1D, 2L and 3L

1L 1D 2L 3L
Formula C24H46N28O7Zn4 C24H46N28O7Zn4 C24H44N28O8Zn4 C28H52N28O6Zn4
Formula weight 1100.45 1100.45 1114.43 1138.54
T/K 293(2) 293(2) 293(2) 293(2)
Crystal system Monoclinic Monoclinic Monoclinic Monoclinic
Space group P21 P21 P21 P21
a/Å 10.185(4) 10.175(4) 10.110(5) 10.2303(3)
b/Å 21.488(9) 21.481(10) 21.362(10) 21.4402(6)
c/Å 10.501(5) 10.493(5) 10.475(5) 11.1573(4)
a/ 90 90 90 90
b/ 93.174(8) 93.144(9) 93.970(6) 91.259(3)
g/ 90 90 90 90
V/Å3 2294.7(17) 2290.0(18) 2256.8(19) 2446.65(13)
Z 2 2 2 2
Dcalc/g cm3 1.593 1.596 1.640 1.546
m/mm1 2.137 2.142 2.176 2.810
F(000) 1124.0 1124.0 1136.0 1168.0
R1 0.0643 0.0685 0.0733 0.0446
wR(F2) 0.1538 0.1590 0.1810 0.1304
GOF 0.965 1.046 1.019 1.017
Flack 0.24(5) 0.33(5) 0.21(5) 0.17(7)

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1.972 to 2.118 Å, respectively. The L-Ala ligand is coordinated to

two Zn centers. All the 5-mtz ligands adopt similar coordination
mode of 2-methylimidazole, using two N atoms to coordinate
two Zn atoms. The Zn/Zn distances linked by 5-mtz ligands
range from 6.036 to 6.227 Å. In comparison, short Zn/Zn
distances linked by L-Ala ligands ranging from 5.189 to 5.199 Å
are observed. All the Zn atoms were linked by 5-mtz ligands to
form a layer (Fig. 2c), which can be simplied as a 3-connected
(63) net. The L-Ala ligands further link adjacent layers to form
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a 3D framework (Fig. 1b). Notably, a remarkably structural

feature in 1L is the presence of three-dimensional 4-connected
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ABW network. As mentioned above, both of the L-Ala and 5-mtz

act as m2-bridging ligands. Each Zn center can be successfully
reduced as a 4-connected node. As a result, the whole frame-
work can be topologically represented as a uninodal 4-con-
nected zeotype ABW topology by considering L-Ala and 5-mtz as
simple linkers (Fig. 2a and d). Two kinds of channels along the Fig. 3 Enantioselective recognition of carvone in ethanol solutions, (a)
a-axis are observed in the structure of 1L. The small channel is 1L; (b) 1D; (c) 2L; (d) 3L.
from the typical double zigzag chain (DZC) which is well known
in zeolite structures (Fig. 2b). The large channel with dimension
of ca. 5.5  11.2 Å are lled by the structurally ordered DMF porosity of 1L to 3L was conrmed by the reversible CO2 sorp-
molecules. Strong N–H/O hydrogen bonding interactions (dN– tion measurements at 195 K (Fig. S3†). The Langmuir and BET
O ¼ 2.753 Å and 2.945 Å) are observed between the amino ligand surface areas of 1L were 302 m2 g1 and 294 m2 g1, respec-
and the DMF guest (Fig. 1b). The solvent-accessible volume of tively. The Langmuir and BET surface areas for 2L were 377 m2
ca. 32.1% was calculated by the PLATON program.14 The g1 and 364 m2 g1, respectively. 3L has the largest Langmuir
solvent-accessible volume for 2L and 3L were 30.7% and and BET surface areas (672 m2 g1 and 658 m2 g1, respectively),
30.1%, respectively. which may be assigned to the isopropyl group connected to a-C
of amino acid enlarge the channel (Fig. 1).
X-ray powder diffraction and thermal analysis
The powder X-ray diffraction patterns conrm the phase purity Chiral recognition of carvone
of the bulk products and also demonstrate that activated Since 1L, 1D, 2L and 3L are homochiral frameworks, we are
frameworks of 1L, 1D, 2L, 3L remain unchanged aer gas interested in their potential properties on chiral recognition of
sorption measurements (Fig. S1†). Thermal gravimetric analysis carvone. A solution of D-carvone or L-carvone in ethanol with the
(TGA) shows that 1L, 1D, 2L, 3L can be stable up to ca. 230  C same concentration (102 mol L1) and amount (2 mL) were
under the N2 atmosphere (Fig. S2†). placed in the cells. Then the same amounts of the as-
synthesized samples of 1L, 1D, 2L and 3L were added respec-
Gas absorption measurement tively, and the circular dichroism (CD) signal was recorded. For
Gas-adsorption measurements of 1L to 3L were performed on 1L, 2L and 3L (Fig. 3a, c and d), the CD intensities of solutions
a Micromeritics ASAP 2020 surface-area and pore-size analyzer. decreased with the increased samples, however, the intensity of
The samples were activated by solvent exchange with ethanol D-carvone decreased more drastically than that of L-carvone. The

followed by evacuation at 60  C for 5 hours. The permanent result means that the interactions between the samples based
on L-amino and D-carvone are stronger than the interactions
between the samples based on L-amino and L-carvone. For 1D
(Fig. 3b), the intensity of L-carvone decreased more drastically
than that of D-carvone, which indicates the stronger interactions
between 1D and L-carvone. The samples (about 250 mg) based
on L-amino acids exhibit separation ee values of 1L, 2L and 3L
are 18.6%, 43.2% and 25.8%, respectively. The largest separa-
tion ability of 2L may be attributed to the –OH groups, which
promote the interaction between 2L and carvone.

Conclusions
In summary, we rst constructed a series of homochiral ZMOFs
Fig. 2 (a) The simplified L-alanine and 5-methyltetrazole; (b) the DZC with ABW topology by employing enantiopure amino acids with
chain in 1L; (c) 3-connected net in 1L; (d) the ABW topology of 1L. tetrazolate ligands. These materials show permanent

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