Weak interactions in imidazole-containing zinc(II)-based metal–organic frameworks

Article abstract of DOI:10.1002/jccs.202000106

The self-assembly of the two zinc(II) metal–organic frameworks, [Zn₂(L)(bdc)₂]·3MeOH·4H₂O}_n (1, L = 2-(pyridin-4-yl)-3H-imidazo[4,5-c]pyridine, H₂bdc = 1,4-benzenedicarboxylic acid) and [Zn₂(L)(bdc)₂]·2DMF·H₂O}_n (2), was achieved under mild reaction conditions. Both compounds 1 and 2 were structurally characterized by single-crystal X-ray diffraction analysis. Interestingly, the coordination modes of the ligand L in two structures are entirely different. Compounds 1 and 2 were made up of paddle wheel-shaped {Zn₂(O₂C)₄} secondary building unit (SBU) clusters, which adopted three-dimensional structures with a pcu topology. Rich weak interactions were observed in the structures of both 1 and 2. The uncoordinated imidazole and pyridine moieties exhibited electron donor–acceptor interactions, π–π stacking, hydrogen bonding, and CH–π interactions. These interactions also facilitated the abilities of the framework to adsorb CO₂ molecules. Gas adsorption studies revealed that compound 1 selectively adsorbed CO₂ (131.1 cm³/g) over N₂ (23.5 cm³/g) and H₂ (36.5 cm³/g) at a pressure of 1 atm.

Full text of DOI:10.1002/jccs.202000106

Received: 13 March 2020
Revised: 11 June 2020
Accepted: 20 June 2020
DOI: 10.1002/jccs.202000106
S P E C I A L I S S U E P A P E R
Weak interactions in imidazole-containing zinc(II)-based
metal–organic frameworks
1
,2
1
3
3
Hsin-Wei Wu
| Li-Wei Lee | Pounraj Thanasekaran | Cing-Huei Su
|
3
2
1,3
Yen-Hsiang Liu | Tsung-Mei Chin | Kuang-Lieh Lu
1
Institute of Chemistry, Academia Sinica,
Abstract
Taipei, Taiwan
2
The self-assembly of the two zinc(II) metal–organic frameworks, [Zn (L)
Department of Chemistry, Chinese
2
Culture University, Taipei, Taiwan
(bdc) ]Á3MeOHÁ4H O} (1, L = 2-(pyridin-4-yl)-3H-imidazo[4,5-c]pyridine,
2
2
n
3
Department of Chemistry, Fu Jen
H bdc = 1,4-benzenedicarboxylic acid) and [Zn (L)(bdc) ]Á2DMFÁH O} (2),
2
2
2
2
n
Catholic University, New Taipei City,
Taiwan
was achieved under mild reaction conditions. Both compounds 1 and 2 were
structurally characterized by single-crystal X-ray diffraction analysis. Interest-
ingly, the coordination modes of the ligand L in two structures are entirely dif-
ferent. Compounds 1 and 2 were made up of paddle wheel-shaped {Zn (O C) }
Correspondence
Kuang-Lieh Lu, Institute of Chemistry,
Academia Sinica, Taipei 115, Taiwan.
Email: kllu@gate.sinica.edu.tw
2
2
4
secondary building unit (SBU) clusters, which adopted three-dimensional
structures with a pcu topology. Rich weak interactions were observed in the
structures of both 1 and 2. The uncoordinated imidazole and pyridine moieties
exhibited electron donor–acceptor interactions, π–π stacking, hydrogen bond-
ing, and CH–π interactions. These interactions also facilitated the abilities of
Yen-Hsiang Liu, Department of
Chemistry, Fu Jen Catholic University,
New Taipei City 242, Taiwan.
Email: chemyhl@gmail.com
the framework to adsorb CO molecules. Gas adsorption studies revealed that
Tsung-Mei Chin, Department of
Chemistry, Chinese Culture University,
Taipei 111, Taiwan.
2
3
3
compound 1 selectively adsorbed CO (131.1 cm /g) over N (23.5 cm /g) and
2
2
3
H (36.5 cm /g) at a pressure of 1 atm.
2
Email: tmchin@faculty.pccu.edu.tw
K E Y W O R D S
Funding information
Ministry of Science and Technology,
Taiwan, Grant/Award Number: MOST-
coordination mode, metal–organic frameworks, structure, weak interactions, zinc
106-2113-M-001-032; Academia Sinica
[
14–16]
1
| INTRODUCTION
properties while still maintaining their porosity.
This type of ligand is also an excellent model for exam-
ining weak interactions in MOFs due to their intrinsic
hydrogen bonding and π–π stacking interactions. In
addition, weak interactions of MOFs with small mole-
cules such as H , CH , and CO have also attracted
It is well known that metal–organic frameworks (MOFs)
have a number of unique features, which make them
[1–13]
extraordinarily applicable for use in a variety of fields.
Among those features, rich weak interactions in MOFs
are highly significant in terms of tuning the orientations
of the building units, stabilizing the overall structures,
influencing the functionalities, and the potential appli-
cations of these materials. Interestingly, the design of a
multifunctional ligand containing imidazole moieties
can be used not only to fabricate MOFs with unique net-
work topologies but can also be utilized to alter their
2
4
2
interest as these MOF–guest interactions facilitate their
[
17–24]
gas adsorption–desorption and sensing capacities.
Although the synthesis and properties of a number of
[
14–16,25–29]
imidazole-containing MOFs have been reported,
the integration of an imidazole group with two pyridine
moieties in a coordinated ligand in an MOF has rarely
[
30–33]
been addressed.
©
2020 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J Chin Chem Soc. 2020;1–7.
http://www.jccs.wiley-vch.de
1

2
WU ET AL.
Here, we report on the selection of a model ligand L
L = 2-(pyridin-4-yl)-3H-imidazo[4,5-c]pyridine), from
dimensional (3D) framework with a pcu topology (Fig-
ure 1b). Due to the large cavity space of the resulting pcu-
type 3D-net, a twofold intepenetration of the 3D network
was observed in 1 (Figure 1c). It is worth noting that a
net-to-net π–π interaction is observed, which serves to
enhance the stability of the interpenetrated network (Fig-
ure 1d). In spite of the interpenetration behavior, a
PLATON analysis of the potential solvent accessible area
indicated that extra-framework spaces (38.9% of the unit
cell volume) are available for the potential inclusion of
guest molecules. It is also worth noting that the imidaz-
ole ring of the bridging L ligand provides multiple N-sites
(Scheme 2, Type I) that are available for hydrogen bond-
ing interactions, as well as electron donor–acceptor inter-
actions (Figure 1e). The imidazole ring carries dual
Bronsted and Lewis acid-base interactions.
(
which two MOFs, [Zn (L)(bdc) ]Á3MeOHÁ4H O} (1,
2
2
2
n
H bdc = 1,4-benzenedicarboxylic acid) and [Zn (L)
2
2
(
bdc) ]Á2DMFÁH O} (2) (Scheme 1), were synthesized.
2
2
n
Interestingly, the coordination modes of the ligand L in
the two products are completely different in each struc-
ture. The multiple N-donor sites of the L ligand play
important roles in enhancing electron donor–acceptor
interactions, π–π stacking, and hydrogen bonding interac-
tions. These interactions allow compound 1 to display a
high adsorption capacity and good selectivity for CO
131.1 cm /g) over N (23.5 cm /g) and H (36.5 cm /g) at
2
3
3
2 2
3
(
a pressure of 1 atm.
2
| RESULTS AND DISCUSSION
Compounds 1 and 2 were self-assembled from the reac-
tion of Zn(NO ) Á6H O, 2-(pyridin-4-yl)-3H-imidazo[4,5-
2.2 | Structural description of {[Zn (L)
2
(bdc) ]Á2DMFÁH O} (2)
3
2
2
2
2
n
c]pyridine (L) and 1,4-benzenedicarboxylic acid (H bdc)
2
in a H O/MeOH/DMF solution (using THF buffer for 2
only) under mild reaction conditions (Scheme 1).
A single-crystal X-ray diffraction analysis revealed that
compound 2 crystallizes in a monoclinic unit cell with
space group C2/c. The crystallographic asymmetric unit
2
2
−
contains a zinc (II) cation, one bdc ligand, half of an L
ligand, and a guest DMF molecule, as well as disordered
water molecules. Because of the disordered nature of the
guest molecules, only the DMF molecule was located on
the electron density map. The assignment of the disor-
dered guest water molecules was further examined by
thermogravimetric measurements. Similar to compound
1, two zinc ions are coordinated by four carboxylate
2
.1 | Structural description of {[Zn (L)
2
(bdc) ]Á3MeOHÁ4H O} (1)
2
2
n
A single-crystal X-ray diffraction analysis revealed that
compound 1 crystallizes in a monoclinic unit cell with
space group P2 /c. The crystallographic asymmetric unit
contains two zinc(II) cations, two bdc ligands, one L
ligand, and disordered guest methanol, as well as water
molecules. Due to the disordered nature, only one of the
methanol molecules was located from the electron den-
sity map. The assignment of the guest molecules was fur-
ther investigated by thermogravimetric measurements.
Two zinc ions are coordinated by four carboxylate groups
1
2
−
2
−
groups from the bdc ligands to form a Zn (O C) pad-
2
2
4
dle wheel-shaped SBU. Two L ligands are coordinated to
the zinc centers through the axial position of the paddle
wheel-shaped SBU, leading to a 6-connecting node and a
three-dimensional framework with a pcu topology (Fig-
ure 2). Unlike compound 1, the imidazole N-sites of the L
ligand participate in the coordination with zinc centers
instead of pyridyl groups (Scheme 2, Type II). Due to the
short length of the linkages, self-interpenetration behav-
ior was not observed for compound 2. The PLATON anal-
ysis of the potential solvent accessible area indicated that
there are extra-framework spaces (51.4% of the unit cell
2
−
from the bdc
ligands to form a Zn (O C) paddle
2 2 4
wheel-shaped secondary building unit (SBU). In addition,
these two zinc ions in the paddle wheel-shaped SBU are
further bound by the pyridine moieties from two sepa-
rated L ligands, leading to a 6-connecting node (Figure 1a,
Scheme 2). As a result, compound 1 presents a three-
SCHEME 1 Route for the
preparation of compounds 1 and 2

WU ET AL.
3
FIGURE 1 Crystal structure of
compound 1. (a) paddle wheel-
shaped structure of the zinc ion
2
−
coordinated with the bdc ligand,
b) three-dimensional structure of
the zinc ion coordinated with the
(
2
−
bdc and the L ligand, (c) twofold
interpenetration of the 3D network,
(
d) net-to-net π–π interaction in the
interpenetrated network, and (e)
hydrogen bonding interactions and
electron donor–acceptor interactions
SCHEME 2 Multiple N-donor sites of the ligand L. Type I is
observed in compound 1, whereas Type II appears in compound 2
FIGURE 2 Crystal structure of compound 2. (a) Paddle
wheel-shaped 6-connecting node of 2, (b) perspective view of the
volume), which are potentially available for the inclusion
of guest molecules. Although the coordination mode of
the bridging ligand L in compound 2 is different from
that in 1 (Scheme 2), the uncoordinated pyridyl ring in 2
is also available for hydrogen bonding interactions, as
well as electron donor–acceptor interactions (Figure 2d).
3D network of 2, (c) topological view of the network of 2, and (d)
graphical representation of the uncoordinated N-site of the pyridyl
ring engaging electron donor–acceptor and hydrogen bonding
interactions
mode is observed in compound 1, where the long-end N-
donor sites from two separated pyridines provide the long
linkage that connects the two paddle wheel units. This
type of coordination creates a large void in the cubic unit
of a pcu net, leading to the formation of a twofold inter-
penetrated 3D network. Extensive net-to-net π–π interac-
tions in the interpenetrated network are observed, which
function to stablize the interpenetrated structure of 1. In
addition, hydrogen bonding and electron donor–acceptor
2
.3 | Comparison of the structures in
compounds 1 and 2
It would be interesting to compare the structures of com-
pounds 1 and 2 because the coordination modes of L are
entirely different. The ligand L contains multiple N-
donor sites. As shown in Scheme 1, a type I coordination

4
WU ET AL.
interactions between methanol guest molecules and the
uncoordinated imidazole moiety are apparent.
respectively, at 1 atm with irreversible type II isotherms
[
22,34]
(Figure S7).
The CO adsorption of compound 1 at
2
It is particularly interesting that the type II coordina-
tion mode of the L ligand appears in compound 2. In this
case, the side-on linkage through the imidazole moiety of
the L ligand is bonded to two metal centers, as shown in
Scheme 1. To the best of our knowledge, this constitutes
the first report of this type of coordination mode. The
length through the side-on imidazole linkages appeared
to be too short so that self-interpenetration of the net-
work does not occur. This finally creates a large extra-
framework space in the resulting pcu net of 2, which can
accommodate large guest molecules, such as DMF.
Although π–π stacking interactions are not observed in
the structure of 2, electron donor–acceptor and hydrogen
bonding interactions between the uncoordinated N-site
of the pyridyl ring and the DMF molecule are evident
1 atm and controlled temperature at 195 K showed typi-
cal type I isotherm. Measurement of the CO sorption iso-
2
therm at 195 K revealed that compound 1 has a relatively
3
higher CO loading of 131.1 cm /g, while at 273 and
2
3
298 K, the values were 27.5 and 19.4 cm /g, respectively
(Figure 3). The enhancement of CO uptake for 1 at
2
195 K can be attributed to the lone pair of electrons in
the uncoordinated ─N and ─NH moieties from the ligand
L in the channels that can induce electron donor–acceptor
and hydrogen bonding interactions with CO molecules.
2
The value for the uptake of CO for compound 1 is compa-
2
rable with those of many other well-known Zn(II)- and Cd
[
13,23,24,35–42]
(II)-based MOFs.
We therefore propose that
the CO is trapped inside the channel of 1 via interactions
2
of the ─N and ─NH moieties of the ligands with CO2,
(Figure 2d).
leading to the formation of a hysteresis in type I isotherm,
thereby preserving CO molecules.
2
2
.4 | Thermogravimetric and PXRD
analyses
3 | EXPERIMENTAL SECTION
3.1 | Materials and instruments
Thermogravimetric analyses (TGA) analyses were per-
formed for compounds 1 and 2 in an attempt to access
the thermal stability and structural variation as a func-
tion of temperature. The thermogravimetric analysis of 1
showed that solvent molecules are eliminated from the
network (calcd 16.2%, found 16.1%), which corresponds
All chemicals were purchased commercially and were
used as received without further purification. Infrared
spectra were recorded on a Perkin-Elmer Paragon 1000
−
1
FT-IR spectrophotometer in the region 4000–400 cm .
Powder X-ray diffraction measurements were performed
at room temperature using a Siemens D-5000 diffractom-
eter at 40 kV and 30 mA for Cu Kα radiation
to the loss of H O and MeOH guest molecules when the
temperature is increased from room temperature to about
2
ꢀ
1
60 C (Figure S5). Regarding compound 2, after the loss
ꢀ
of the guest H O and DMF molecules (calcd 15.8%, found
(λ = 1.5406 Å) with a step size of 0.02 in θ and a scan
2
ꢀ
1
5.8%) at a temperature of about 100–200 C, the structure
speed of 1 s per step size. Thermogravimetric analyses
were performed in an atmosphere of nitrogen with a
Perkin-Elmer TGA-7 TG analyzer. BET analyses were
ꢀ
was maintained until the temperature reached 300 C,
after which, it began to decompose (Figure S5). The
experimentally obtained PXRD patterns for compounds 1
and 2 were consistent with the simulated patterns calcu-
lated from the single-crystal data (Figure S6).
2.5 | Gas adsorption properties and
selectivity
Inspired by the microporous features and uncoordinated
N-functionalized pores, compound 1 was examined as a
candidate for the selective adsorption of gas molecules.
Calculations indicated that the porosity of compound 1
was 38.9%. The Brunauer–Emmett–Teller (BET) surface
area and Langmuir surface area were determined to be
2
4
1.7 and 110.9 m /g, respectively. The results of sorption
studies revealed that compound 1 exhibited low N and
H uptake capacities of 23.5 and 36.5 cm /g at 77 K,
2
FIGURE 3 Adsorption isotherms of CO of 1 measured at a
temperature of 195, 273, and 298 K
2
2
3

WU ET AL.
5
investigated with a Micrometrics ASAP 2020 system
using nitrogen and hydrogen as the adsorbates at 77 K
and carbon dioxide as the adsorbate at 195, 273,
and 293 K.
5.0 mg, 0.03 mmol), followed by the addition of tetrahy-
drofuran (THF). The resulting solution was sealed in a
closed glass tube, which was then allowed to stand at
room temperature for 1 month, whereupon colorless rect-
angular crystals of compound 2 were formed. The solid
products were isolated on a filter and dried in air. IR
−
1
3
.2 | Preparation of 2-(pyridin-4-yl)-3H-
imidazo[4,5-c]pyridine (L)
(KBr, cm ): 3419, 3098, 2930, 2863, 1957, 1673, 1628,
1502, 1323, 1255, 1173, 1149, 1095, 1063, 1015, 887, 823,
749, 701, 664, 596, 573, 545.
The ligand 2-(pyridin-4-yl)-3H-imidazo[4,5-c]pyridine (L)
[
43]
was synthesized as reported previously (Scheme S2).
In a typical run, the ligand L was prepared by heating a
mixture of pyridine-3,4-diamine (1.3 g, 11.9 mmol), iso-
nicotinic acid (1.6 g, 12.9 mmol), and polyphosphoric
3.5 | Crystallographic measurements
Single crystals of 1 and 2 suitable for X-ray diffraction
ꢀ
acid (15 g, 16.0 mmol) at 180 C for 12 hr under a nitro-
were placed in a cooled stream of N gas at 200 K and
2
gen atmosphere. The resulting mixture was then cooled
to room temperature followed by the addition of 50 ml of
296 K, respectively, for intensity data collection on a
Bruker Kappa CCD diffractometer with graphite mono-
chromated Mo-Kα (λ = 0.71073 Å) radiation. Data reduc-
tion included absorption corrections by the MULTISCAN
H O. The pH of the resulting solution was then adjusted
2
to 7 with ammonia, which resulted in the formation of a
precipitate. Colorless powdered products were obtained
after recrystallization. Yield: 75% (1.8 g, 8.9 mmol). IR
[
44]
method, using the HKL SCALEPACK
and
[
45]
SADABS.
Crystal data and experimental details are
−
1
(
1
KBr, cm ): 3240, 1625, 1603, 1579, 1549, 1457, 1438,
given in Table 1. The X-ray structure was determined by
direct methods and difference Fourier techniques and
refined by full-matrix least squares, using the SHELXL97
1
387, 1368, 1243, 817, 766. H NMR (300 MHz, CD OD-
3
d4, ppm): δ = 7.68 (d, 1H), 8.14 (d, 2H), 8.26 (d,1H), 8.70
d, 2H), 8.9 (s, 1H).
[
46]
(
program.
All nonhydrogen atoms were refined aniso-
tropically. The C-bound and N-bound H atoms were
placed in the calculated positions and refined by the rid-
ing model approximation. Due to the uncertainty in
locating the disordered guest molecules, only some of the
guest molecules were located from the difference Fourier
map in compounds 1 and 2. The crystallographic data for
1 and 2 were deposited at the Cambridge Crystallo-
graphic Data Centre; the deposition numbers for 1 and 2
are CCDC 1990125 and 1990126, respectively.
3
3
.3 | Synthesis of [Zn (L)(bdc) ]Á
2
2
MeOHÁ4H O} (1)
2
n
A total of 2 ml of H O/MeOH (1:1 vol/vol) mixture of Zn
2
(
3
NO ) Á6H O (8.9 mg, 0.03 mmol) and 2-(pyridine-4-y1)-
3
2
2
H-imidazo[4,5-c]pyridine (L, 6.1 mg, 0.03 mmol) was
dissolved in 2 ml of a DMF/MeOH (1:1 vol/vol) solution
containing 1,4-benzenedicarboxylic acid (H bdc, 5.0 mg,
2
0
.03 mmol), sealed in a closed glass tube, and then heated
ꢀ
at 50 C for 48 hr in a water bath. Colorless block-shaped
4 | CONCLUSIONS
crystals of compound 1 were formed in 31% yield
(
7.3 mg, based on Zn(NO ) Á6H O). The solid products
In this work, we report on the successful synthesis of two
Zn-based MOFs from an imidazole derivative and a
dicarboxylate linker under mild reaction conditions. The
imidazole moiety exhibits two different coordination
modes with respect to the Zn metal centers, leading to
the formation of structurally different compounds, that
is, 1 and 2. Although the coordination modes of the imid-
azole group are very different, rich weak interactions
including electron donor–acceptor interactions, π–π stac-
king, hydrogen bonding, and CH–π interactions occur in
the structures. These weak interactions not only dictate
the topology and stabilize the final structures but also
facilitate the adsorption of gas within the porous MOFs.
Compound 1 showed good selectivity for CO over N
3
2
2
−
1
were isolated on a filter and dried in air. IR (KBr, cm ):
3
1
8
392, 3170, 3098, 2864, 2810, 1663, 1637, 1504, 1436,
293, 1254, 1227, 1176, 1152, 1095, 1066, 1016, 934, 885,
24, 746, 715, 662, 610, 596, 548.
3
2
.4 | Synthesis of [Zn (L)(bdc) ]Á
2
2
DMFÁH O} (2)
2
n
Two ml of a H O/MeOH (1:1 vol/vol) solution containing
2
Zn(NO ) Á6H O (8.8 mg, 0.03 mmol) and 2-(pyridine-4-
3
2
2
y1)-3H-imidazo[4,5-c]pyridine (L, 5.9 mg, 0.03 mmol)
was dissolved in 2 ml of DMF/MeOH (1:1 vol/vol) solu-
2
2
tion containing 1,4-benzenedicarboxylic acid (H bdc,
and H due to hydrogen-bonding interaction as well as
2
2

6
WU ET AL.
TABLE 1 Crystal data and structure refinement for
compounds 1 and 2
electron donor–acceptor interaction between the CO2
and N atoms of the MOF.
Compound
1
2
ACKNOWLEDGMENTS
Empirical
formula
C
56
H
40
N
8
O18Zn
4
C
33 29 6 2
H N O10Zn
We gratefully acknowledge the Academia Sinica and the
Ministry of Science and Technology (grant number
MOST-106-2113-M-001-032), Taiwan, for the financial
support.
Formula weight
Temperature
1,374.44
200 (2)
800.36
296 (2)
(
K)
Wavelength (Å)
Crystal system
Space group
0.71073
0.71073
ORCID
Monoclinic
P2 /c
Monoclinic
C2/c
Kuang-Lieh Lu https://orcid.org/0000-0002-5529-7126
1
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R
int
0.0422
0.0403
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c (Å)
10.9546(5)
10.9340(4)
30.2273(11)
93.624(2)
3,613.3(2)
2
23.3639(12)
14.4683(7)
16.1959(8)
128.345(2)
4,293.8(4)
4
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3
ρ
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1.263
1.238
1.170 mm−1
1704303.
1.376 mm−
1
Absorption
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[
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F(000)
1,392
1,636
Crystal size
0.42 × 0.21 × 0.04
0.35 × 0.24 × 0.18
(
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ꢀ
ꢀ
Range for data
collection
1.86–25.00
1.79–25.14
Limiting indices −12 < =h < =9,-
2 < =k < =12,
35 < =l < =35
−27 < =h < =27,
-16 < =k < =17,
−19 < =l < =15
[
[
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1
−
[
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Reflections
collected
24,510
14,803
Reflections
unique
6,308
3,798
[
[
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3
60, 77.
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Completeness
to θ
99.6%
98.7%
2
Max. and min.
Transmission
0.9470 and 0.5958
0.8170 and 0.6849
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6,308/0
388
3,798/0
219
2
, 218.
No. of
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on F
Final R indices
R1 = 0.0444
wR2 = 0.1027
R1 = 0.0691
wR2 = 0.1931
(
I > 2σ(I))
R indices (all
data)
R1 = 0.0618
wR2 = 0.1078
R1 = 0.0753
wR2 = 0.1984
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–F
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