Amino functionalized Zn/Cd-metal-organic frameworks for selective CO2 adsorption and Knoevenagel condensation reactions

Article abstract of DOI:10.1039/c9dt00391f

Two amino functionalized Metal-Organic Frameworks (MOFs), {[Zn(Py₂TTz)(2-NH₂-BDC)]·(DMF)}_n (1) and {[Cd(Py₂TTz)(2-NH₂-BDC)]·(DMF)·0.5(H₂O)}_n (2) (where Py₂TTz = 2,5-bis(4-pyridyl)thiazolo[5,4-d]thiazole, 2-NH₂-BDC = 2-amino-1,4-benzenedicarboxylate, and DMF = N,N-dimethylformamide), were synthesized and characterized using the primary ligand 2-amino-1,4-benzenedicarboxylic acid (2-NH₂-H₂BDC) and the auxiliary ligand 2,5-bis(4-pyridyl)thiazolo[5,4-d]thiazole (Py₂TTz). They possess similar 2-fold interpenetrated three-dimensional bipillared-layer framework structures composed of typical binuclear metal nodes, 2-NH₂-BDC two-dimensional layers and Py₂TTz bipillars. Notably, thiazole nitrogen atoms and pendant -NH₂ groups are present in channels in the two frameworks. Given their good chemical stabilities, high thermal stabilities, and exposed nitrogen sites, gas adsorption and catalytic experiments of the two MOFs were performed. The results demonstrate that MOF 2 can selectively adsorb carbon dioxide gas; moreover, the two MOFs can be employed as recyclable heterogeneous catalysts for Knoevenagel condensation reactions under solvent-free conditions.

Full text of DOI:10.1039/c9dt00391f

View Article Online
View Journal
Dalton
Transactions
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Z. Zhai, S. Yang, Y.
Lv, C. Du, L. Li and S. Zang, Dalton Trans., 2019, DOI: 10.1039/C9DT00391F.
Volume 45 Number
1
7
January 2016 Pages 1–398
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Dalton
Transactions
An international journal of inorganic chemistry
www.rsc.org/dalton
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
rsc.li/dalton

Page 1 of 9
Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
View Article Online
DOI: 10.1039/C9DT00391F
Journal Name
ARTICLE
Amino Functionalized Zn/Cd- Metal−Organic Frameworks for
Selective CO Adsorption and Knoevenagel Condensation Reaction
2
Zhi-Wei Zhai,a,b Shuang-Hua Yang, Ya-Ru Lv, Chen-Xia Du, Lin-Ke Li, Shuang-Quan Zang
b
a
a
*a
*a
Received 00th January 20xx,
Accepted 00th January 20xx
Two amino functionalized Metal−Organic Frameworks (MOFs), {[Zn(Py
2
TTz)(2-NH
2
-BDC)]·(DMF)}
n
(1), {[Cd(Py
2-amino-1,4-
benzenedicarboxylate, and DMF = N,N-dimethylformamide), were synthesized and characterized, using primary ligand 2-
amino-1,4-benzenedicarboxylic acid (2-NH -H BDC) and auxiliary ligand 2,5-bis(4-pyridyl)thiazolo[5,4-d]thiazole (Py TTz).
They possess similar 2-fold interpenetrated three-dimensional bipillared-layer framework structures composed of the
typical binuclear metal nodes, 2-NH -BDC two-dimensional layers and Py TTz bipillars. Notably, the thiazole nitrogen atoms
and pendant −NH groups are present in channels in the two frameworks. Given that their good chemical stabilities, high
2 2
TTz)(2-NH -
DOI: 10.1039/x0xx00000x
BDC)]·(DMF)·0.5(H O)} (2), (where Py TTz 2,5-Bis(4-pyridyl)thiazolo[5,4-d]thiazole, 2-NH -BDC =
=
2
n
2
2
www.rsc.org/
2
2
2
2
2
2
thermal stabilities, and exposed nitrogen sites, gas adsorption and catalytic experiment of the two MOFs were investigated.
The results demonstrate that MOF 2 can selectively adsorb gas carbon dioxide, and moreover, the two MOFs can be
employed as recyclable heterogeneous catalyst for Knoevenagel condensation reaction under solvent-free conditions.
the natural gas purification and the flue gas separation are also
4
3-46
Introduction
As one of the most promising crystalline materials,
metal−organic frameworks (MOFs) have attracted tremendous
attention because of their permanent porosities, diversities,
important topics relating CO selective adsorption.
Hence, it
is imperative to develop materials with the capability of
selective adsorption CO . Fortunately, MOFs materials with
2
2
nitrogenous functional groups might be one of the best
candidates as selective adsorbent. It is reported that
uncoordinated nitrogen atoms can offer openly accessible
1
-5
and designabilities in the past decades,
which display
6
-
extensive potential applications in gas adsorption/separation,
4
9-51
Lewis basic sites for CO
MOFs containing –NH groups could generate easy-on/easy-off
reversible CO adsorption equilibrium with selectivity.
Moreover, the presence of uncoordinated nitrogen sites and –
2
binding in MOFs.
Additionally,
1
2
chemical sensing,13-23 opto-electronic materials,
24-26
2
7-31
32-
2
pollutants adsorption/removal,
heterogeneous catalysis,
5
2-57
3
5
2
etc. Accordingly, design and synthesis of the performance
superior and multifunctional MOFs have been one of the
research hotspots. However, it is very difficult to obtain the
targeted structure because many factors will cause the diverse
structure of MOFs, such as the coordination mode of organic
linker, the nature of metal ion, as well as the synthesis condition.
Therefore, combining the typical secondary building units (SBUs)
with customized linkers has become a common and effective
strategy for the construction of the desired MOFs, which
provide a versatile platform for accomplishing the targeted
applications through introducing suitable functional groups.
As is well known, carbon dioxide (CO ) is one of the major
greenhouse gases resulting in the dramatic environmental
issues (global warming), which is able to be alleviated
2
NH groups might afford an opportunity to perform base-
catalyzed reactions such as Knoevenagel condensation, which is
one of the classic and versatile C–C bond forming reactions in
However, such functionalization is not
easy to realize owing to the strong coordination abilities of
nitrogen atoms. So far, only a few MOFs with nitrogenous
functional groups have been obtained by direct synthesis.
In the pursuit of performance superior multifunctional
materials for CO adsorption, catalysis as well as other
applications, we have been working on design and synthesis of
the MOFs with nitrogenous functional groups. Based on our
5
8-63
synthetic chemistry.
6
4-67
3
6-39
2
2
6
8,69
previous studies,
by nitrogenous linkers 2,5-bis(4-pyridyl)thiazolo[5,4-d]thiazole
Py TTz) and 2-amino-1,4-benzenedicarboxylic acid (2-NH
BDC) will provide a multifunctional platform for adsorbing
CO selectively and catalyzing Knoevenagel reaction effectively.
Herein, assembling Py
Zn(II)/Cd(II), two MOFs, {[Zn(Py
we envisioned that the MOFs constructed
4
0-42
effectively by the CO
2
capture and storage.
Furthermore,
(
2
2
-
H
2
a
College of Chemistry and Molecular Engineering, Zhengzhou University,
Zhengzhou, 450001, P. R. China.
2
1
0
b
2
TTz and 2-NH
TTz)(2-NH
-BDC)]·(DMF)·0.5(H O)}
,5-Bis(4-pyridyl)thiazolo[5,4-d]thiazole, 2-NH
2
-H
2
BDC with d metal ions
-BDC)]·(DMF)} (1),
(2), (where Py TTz =
-BDC = 2-amino-
School of Environmental Engineering and Chemistry, Luoyang Institute of
Science and Technology, Luoyang 471023, P. R. China.
E-mail: lilinke@zzu.edu.cn, zangsqzg@zzu.edu.cn
2
2
n
{
2
[Cd(Py
2
TTz)(2-NH
2
2
n
2
†Electronic Supplementary Information (ESI) available: Crystallographic data, TGA,
PXRD patterns, IR spectra, gas adsorption date for complexes 1 and 2; PXRD
2
patterns, IR spectra, SEM for complexes 1a and 2a. CCDC numbers 1882223 and 1,4-benzenedicarboxylate, and DMF = N,N-dimethylformamide),
1
882224 for complexes 1 and 2. See DOI: 10.1039/x0xx00000x
have been obtained successfully. They possess similar three-
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Page 2 of 9
ARTICLE
Journal Name
dimensional (3D) bipillared-layer framework structures Synthesis of {[Cd(Py
composed of the typical binuclear metal nodes, 2-NH -BDC two-
dimensional (2D) layers and Py TTz bipillars. Interestingly, the
numerous thiazole nitrogen atoms and pendant −NH groups
are exposed to their channels, which provide a good platform
to explore CO adsorption and base-catalyzed reactions. The
experimental results demonstrate that MOF 2 can selectively
adsorb CO , and moreover, both MOFs can be employed as
2
TTz)(2-NH
According to the aforementioned procedure except that
Zn(NO ·6H O was replaced by Cd(NO ·4H O (10 mg, 0.032
mmol), the block-shaped light yellow crystals of 2 were
obtained. Crystals were filtered, washed with DMF, and dried in
View Article Online
2 2 n
-BDC)]·(DMF)·0.5(H O)} (2)
DOI: 10.1039/C9DT00391F
2
2
)
3 2
2
)
3 2
2
2
2
2
air (8.8 mg, 66% yield based on Py TTz ligand). Elemental
analysis (%) calcd for C25 Cd: C 44.82, H 3.16, N 12.54,
21 6 5.5 2
H N O S
2
S 9.57; found: C 44.86, H 2.94, N 12.45, S 9.45. Main infrared
efficient heterogeneous catalysts for the Knoevenagel
condensation reaction. Furthermore, the substituent effects for
various benzaldehyde derivatives in Knoevenagel reaction were
also examined systematically.
-1
spectral data (KBr, cm ): 3452 (s), 3409 (s), 3361 (s), 3297 (s),
3
054 (w), 3031 (w), 2921 (w), 2852 (w), 1670 (m), 1602 (s), 1560
s), 1506 (m), 1444 (m), 1417 (s), 1371 (s), 1323 (m), 1245 (m),
215 (m), 1143 (s), 1091 (m), 1064 (m), 1027 (s), 1012 (m), 823
s), 775 (m), 702 (s), 665 (m), 617 (s), 584 (m), 505 (s). (IR
(
1
(
spectrum is shown in Figure S2).
Experimental
Materials and methods
X-ray Crystallography
Single-crystal X-ray diffraction data of 1 and 2 were collected on
a Rigaku XtaLAB Pro diffractometer with Cu-Kα radiation (λ =
All the chemicals for experiment are commercially available and
used as received without further purification. 2,5-Bis(4-
1
.54178 Å) at 150 K. Crystallographic data reduction were
pyridyl)thiazolo[5,4-d]thiazole
diphenylthiazolo[5,4-d]thiazole (Ph
according to the reported procedures but modified slightly.
Infrared spectra (IR) (KBr pellets) were recorded on a Nexus 870
2
(Py TTz)
and
2,5-
7
2
performed using the program CrysAlisPro. The structures
were solved with direct methods (SHELX), and refined by full-
matrix least squares on F using OLEX2, which utilizes the
2
TTz) were prepared
7
3
7
0,71
2
74
7
5
SHELXL-2013 module. The hydrogen atoms were placed
geometrically. All non-hydrogen atoms were refined
anisotropically. In 2, the guest DMF molecules and water
molecules are too disordered to be modeled properly. So the
diffuse electron densities resulting from these solvent
molecules are removed by using the SQUEEZE routine of
PLATON program to produce solvent-free diffraction intensities
of 2. The guest molecules were quantified through the
elemental analyses and thermogravimetric analyses. So the
final molecular formulae for 1 and 2 were determined. The
relevant crystallographic data are summarized in Table S1.
Selected bond lengths and angles are summarized in Table S2.
CCDC numbers of 1 and 2 are 1882223 and 1882224,
respectively.
-1
FTIR spectrometer in the range of 400−4000 cm . Elemental
analyses (EA) were conducted with a Perkin-Elmer 240
1
elemental analyzer. H NMR spectra were recorded on a Bruker
3
DRX spectrometer (400 MHz) in CDCl . Powder X-ray diffraction
(PXRD) patterns of the samples were recorded in the 2θ = 5−50
°
range on a Bruker D8 Advance diffractometer with Cu Kα
1.5418 Å) at room temperature.
radiation (λ
=
7
6
Thermogravimetric analyses (TGA) were performed on a TA Q50
thermogravimeter from room temperature to 800 °C with a
-1
heating rate of 10 °C·min under Ar atmosphere. Gas sorption
isotherms were measured on BEL-max physisorption analyzer
after the removal of guest molecules by evacuation at 100 °C for
1
2 h. Scanning electron microscope (SEM) images were
acquired using a Zeiss Sigma 500 emission scanning electron
microscope with an accelerating voltage of 2–10 kV.
Catalytic Experiment
Before used as catalysts, 1 and 2 were activated by following
procedure. 1 and 2 were soaked in methanol for 3 days and the
used methanol was replaced 4 times every day. Then, the
samples were collected and dried at 80 °C for 10 h under
vacuum, obtaining activated samples 1a and 2a. The activated
samples (1a and 2a) were employed to catalyze Knoevenagel
condensation reactions with benzaldehyde derivatives and
malononitrile. In typical procedure, benzaldedyde (1 mmol),
malononitrile (2 mmol) and catalyst (1a or 2a) (0.02 mmol) were
added into 10 mL round-bottomed flask and stirred at 60 °C
under solvent-free condition. The process of reaction was
monitored by thin layer chromatography (TLC). After the
reaction finished completely, the yield of desired product was
Synthesis of {[Zn(Py
Zn(NO ·6H O (10 mg, 0.034 mmol), Py
and 2-NH -H BDC (6 mg, 0.033 mmol) were added to the mixed
solvent (2.5 mL, DMF/H O = 4/1) and sonicated for 30 minutes.
Subsequently, the reaction mixture was transferred to a PTFE-
lined stainless-steel vessel, which was placed in the oven and
was kept at 100 °C for 48 h. After cooling to ambient
temperature, needle-shaped yellow crystals were obtained.
Crystals were filtered, washed with DMF, and dried in air (10.8
2
TTz)(2-NH
2
-BDC)]·(DMF)}
n
(1)
)
3 2
2
2
TTz (6 mg, 0.020 mmol)
2
2
2
mg, 87% yield based on Py
calcd for C25 Zn: C 48.90, H 3.28, N 13.69, S 10.44;
found: C 48.49, H 3.19, N 13.46, S 10.14. Main infrared spectral
2
TTz ligand). Elemental analysis (%)
20 6 5 2
H N O S
-1
data (KBr, cm ): 3544 (s), 3455 (s), 3417 (s), 3357 (s), 3056 (w),
031 (w), 2921 (w), 2850 (w), 1668 (m), 1616 (s), 1575 (s), 1444
1
determined by H NMR spectroscopy. The Knoevenagel
3
reactions involving other benzaldehyde derivatives and
malononitrile were also proceeded according to the
aforementioned procedure.
(m), 1421 (m), 1382 (s), 1322 (m), 1259 (m), 1213 (m), 1145
(m),1030 (s), 1091 (m), 1064 (m), 1029 (m), 825 (m), 769 (m),
7
05 (m), 665 (m), 620 (s), 582 (m), 509 (s), 478 (m), 406 (m). (IR
Recyclable Experiment
spectrum is shown in Figure S1).
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 9
Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Journal Name
ARTICLE
To evaluate the recycling ability catalysts, the recycling the range of 2.1512(17) Å − 2.1893(18) Å. The O−VZienw−AOrticlaenOgnllienes
experiments of samples (1a and 2a) as catalyst for the are in the range of 59.46(6)° − 151.72(6)D°O, tI:h1e0.1N0−39Z/nC−9ODTa0n03g9le1Fs
Knoevenagel condensation reaction were investigated. After are in the range of 87.88(6)° − 92.37(6)°, and the N−Zn−N angle
2
−
the Knoevenagel condensation reaction finished, chloroform is 179.70(7)° (Table S2). The deprotonated 2-NH
was charged into the reaction mixture and then the catalyst (1a -bridging ligand, in which the two carboxylate groups adopt
or 2a) was recollected by centrifugation. Subsequently, the two different coordination modes: one adopting μ
recollected catalyst was washed by chloroform three times, bismonodentate bridging mode while the other one adopting
2
-BDC acts as
μ
3
1
1
2
-η :η -
1
1
dried under vacuum at 80 °C for 10 h, and then reused for the
μ
1
-η :η -
bidentate
chelating
mode.
The
two
next round catalytic experiment. The yield of desired product crystallographically equivalent Zn(II) ions are bridged by two
1
was determined by H NMR spectroscopy so as to evaluate the carboxylate groups to form a binuclear secondary building unit
2
−
performance of the recycled catalyst.
(SBU) Zn
ligands along the ac plane to provide a 2D sheet of {Zn
BDC) (Figure 1b). Further, the adjacent 2D sheets are pillared
by Py TTz ligands to construct a 3D bipillared-layer framework
Figure 1c). Because of large voids, the two single 3D networks
2-fold
2
(μ-OCO)
2
, which is further connected by 2-NH
2
-BDC
2
2
(2-NH -
2 n
}
Results and discussion
2
Synthetic Conditions
(
Synthetic conditions of 1 and 2 were investigated systematically. are further intertangled each other to yield
a
The results indicate that temperature, solvent, and the ratio of interpenetrated networks. However, it still exhibits significant
mixed ligands, all have important influences on the target channels along a or c axis (Figure 1d−e). There are two types of
product. Firstly, the temperature plays a crucial role. At 100 °C, channels: pore A decorated with the pendant −NH
2
groups and
1
and 2 have been obtained with good quality. However, no pore B with no −NH groups along c axis (Figure 1e). All the
2
obvious crystals have been gained whether at lower channels are decorated by thiazole nitrogen atoms along a or c
temperature or at higher temperature. Secondly, the solvent axis (Figure 1d−e). Additionally, these channels are occupied by
also affects the quality and the yield of the crystals. In the
2
mixture solvent DMF/H O (2 mL / 0.5 mL), 1 and 2 have been
obtained with good quality and high yield. However, in the
mixture solvent DMF/ethanol (2 mL / 0.5 mL), the purity and
yields of target products are very poor; even no target products
have been obtained in pure DMF, ethanol, H
Last but not least, the ratio of mixture ligands also plays an
important role. When the molar ratio of ligand 2-NH -H BDC to
ligand Py TTz is in the range of 1.5−1.9, the purity and yields of
2
O, respectively.
2
2
2
target products are very good. Above 1.9 or below 1.5, the
purity and yields of target products will all be reduced.
Therefore, the optimum synthetic conditions of 1 and 2 is, the
molar ratio of ligand 2-NH
2
-H
2 2
BDC to ligand Py TTz in the range
2
of 1.5−1.9, mixture solvents DMF/H O (2 mL / 0.5 mL), at 100 °C
for 48 h.
Structure Description
The single-crystal X-ray diffraction analyses illustrate that 1 and
are isostructural, which possess similar nodes and connection
2
modes. However, they crystallize in the different crystal
systems and space groups, which illustrates that the final
structures of MOFs can be influenced by the nature of metal
ions. In view of their structural similarities, only the crystal
structure of 1 is described in detail for the sake of simplicity. The
single-crystal data reveal that 1 is a 3D bipillared-layer
framework composed of the binuclear Zn(II) nodes, 2-NH
2
-
Figure 1. (a) Coordination environment of Zn(II) in 1;
hydrogen atoms and lattice solvent molecules are omitted for
clarity. Symmetry codes: #1 1 - x, - y, 1 - z; #2 1 - x, 1 - y, 1 - z;
#3 0.5 - x, y, 0.5 + z; #4 0.5 + x, - y, 0.5 - z; #5 x, - 1 + y, z. Two
2
−
2
BDC ligands and Py TTz coligands. It crystallizes in the
orthorhombic crystal system with Pccn space group, and the
2
−
asymmetric unit consists of one Zn(II) ion, one 2-NH
ligand, one Py
The Zn(II) center is coordinated by four oxygen atoms from
three 2-NH
-BDC2− ligands and two nitrogen atoms from two
Py TTz ligands to form a distorted octahedron geometry
ZnO ) (Figure 1a). The Zn−O bond lengths are in the range of
.0003(14) Å − 2.3179(16) Å and the Zn−N bond lengths are in
2
-BDC
TTz ligand, and two halves of free DMF molecules. −NH groups in 2-NH -BDC2− is due to its positional disorder.
2
2 2
(b) 2D sheet of the {Zn (2-NH -BDC) } . (c) 3D bipillared-layer
2
2
2 n
2
framework of 1. (d) View of 2-fold interpenetrated 3D
2
framework of 1 along a axis; blue represent −NH group. (e)
2
(
N
4 2
View of 2-fold interpenetrated 3D framework of 1 along c
2
axis; blue represent −NH group.
2
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Page 4 of 9
ARTICLE
Journal Name
the guest molecules DMF, which can be confirmed by the whereas only the channels are decorated with pVeienwdAarntictle−ONnlHine
2
DOI: 10.1039/C9DT00391F
elemental analyses as well as the TG analyses. The calculated groups along b axis (Figure 2d−e).
solvent-accessible volume by PLATON program is
approximately 25.2% after removal of guest DMF molecules.
Interestingly, the pendant −NH
the channels in 2 along b axis, whereas the pendant −NH
2
groups are distributed in all
2
Similarly, 2 is also a 3D bipillared-layer framework structure. groups are only distributed in the half of the channels in 1 along
However, it crystallizes in the monoclinic crystal system with c axis. Additionally, from construction perspective, the major
P2
sheet of the {Cd
and 2-fold interpenetrated 3D framework are shown in Figure 68.402(0)° in 2, respectively (Figure S3). Meanwhile, the bond
1
/n space group. The coordination environment of Cd(II), 2D difference of the two MOFs is the 2D sheet, in which the interior
2
(2-NH -BDC) , 3D bipillared-layer framework, angles of the rhombus-shaped grids are 83.542(0)° in 1 and
2
2 n
}
2
2
2
5
8
a−e. The Cd−O bond lengths are in the range of 2.242(2) Å − lengths of Zn−O and Zn−N in 1 are shorter than the bond lengths
.409(2) Å and the Cd−N bond lengths are in the range of of Cd−O and Cd−N in 2 whereas the N−Zn−N bond angle is bigger
.321(3) Å − 2.340(3) Å. The O−Cd−O angles are in the range of than the N−Cd−N bond angle (Table S2). This might be the
4.93(8)° − 149.18(8)°, the N−Cd−O angles are in the range of reason why they crystallize in the different crystal systems with
4.31(9)° − 100.73(10)°, and the N−Cd−N angle is 170.09(11)° different space groups.
(
Table S2). The channels of 2 are also occupied by guest DMF
Determination of Guest Molecules
molecules and water molecules. Its void volume is
approximately 28.2% of the total crystal volume after removing
the guest molecules by PLATON calculations. All the channels
are decorated by thiazole nitrogen atoms along a or c axis,
On the basis of the crystal data, the molecular formulae of 1 and
2
are preliminarily defined as {[M(Py
2 2 n
TTz)(2-NH -BDC)]·guest}
(M = Zn for 1, Cd for 2), which are electrically neutral.
Furthermore, the occupancies of two DMF molecules in 1
should be 0.5 by elemental analyses and thermogravimetric
analyses, accordingly its exact molecular formula can be defined
2 2 n
as {[Zn(Py TTz)(2-NH -BDC)]·(DMF)} . However, the solvent
molecules in 2 are too disordered to be modeled properly, its
exact molecular formula need be further determined by
elemental analyses and thermogravimetric analyses.
Comparing the found value of elemental analyses for 2 with the
calculated value of elemental analyses for its primary
framework, the found values of N, H element are higher than
their calculated values, which imply the guest molecules
including DMF molecules and H
in the mixed solvent DMF and H
formula of 2 can be further modified as {[Cd(Py
BDC)]·x(DMF)·y(H O)} . According to the found values of C, H
2
O molecules (2 was synthesized
O). Therefore, the molecular
TTz)(2-NH
2
2
2
-
2
n
element for 2, x and y are calculated to be 1 and 0.5,
respectively. Accordingly, the molecular formula of 2 can be
defined as {[Cd(Py TTz)(2-NH -BDC)]·(DMF)·0.5(H O)} . The
2 2 2 n
formulae of the two compounds agree well with their elemental
analyses and thermogravimetric analyses, which indicate that
the formulae for 1 and 2 are accurate.
Powder X-ray Diffraction
The purities of the synthesized bulk samples (1 and 2) were
confirmed by PXRD experiment. As shown in Figures S4 and S5,
experimental patterns of the two as-synthesized samples agree
well with the simulated patterns from their single crystal data,
which indicate that the synthesized bulk samples (1 and 2) are
pure phase. Furthermore, stabilities of 1 and 2 were
investigated in common solvents such as DMF, methanol,
acetone, chloroform, and water. As shown in Figures S4 and S5,
PXRD patterns of 1 and 2 soaked in common solvents for 48 h
are consistent with their origins, which indicate that 1 and 2 are
stable in common solvents. PXRD patterns of the activated
samples 1a and 2a were also measured, which agree well with
the experimental patterns of two as-synthesized samples,
indicating that the frameworks of 1 and 2 still remain constant
Figure 2. (a) Coordination environment of Cd(II) in 2;
hydrogen atoms and lattice solvent molecules are omitted for
clarity. Symmetry codes: #1. 2 - x, 1 - y, 2 - z; #2. 1/2 + x, 3/2 -
y, - 1/2 + z; #3. 1 + x, + y, 1 + z; #4. 3/2 - x, - 1/2 + y, 5/2 - z; #5.
2
−
1
- x, 1 - y, 1 - z. Two −NH
positional disorder. (b) 2D sheet of the {Cd
c) 3D bipillared-layer framework of 2. (d) View of 2-fold
2
groups in 2-NH
2
-BDC is due to its
2
(2-NH -BDC)
2
2 n
} .
(
interpenetrated 3D framework of 2 along a axis; blue
represent amino group. (e) View of 2-fold interpenetrated 3D
framework of 2 along b axis; blue represent amino group.
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 9
Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Journal Name
ARTICLE
after removal of guest DMF molecules and water molecules comparable to the values of many MOF materials without open
View Article Online
DOI: 10.1039/C9DT00391F
79
(
Figures S4 and S5).
metal sites used for CO
However, 1 has almost no uptake for CO
Figure S10), which might be caused by the difference of pore
sizes for the two MOFs. The above results indicate that 2 could
2
selectively adsorbing capture.
2
at 195 K and 273 K
Thermogravimetric Analyses
(
To evaluate their thermal stabilities, thermogravimetric
analyses of 1 and 2 were examined. As shown in Figure S6 and
S7, two compounds have high thermal stabilities. MOF 1
undergoes a gradual weight loss of 11.72% until 343 °C due to
2
be used as effective CO selective adsorption material.
Catalytic Experiment
2
the loss of DMF molecules in the crystal lattice (calculated value The structural rigidities, big channels, decorated −NH groups,
is 11.90%), and then shows a steep mass loss assigned to the and high thermal stabilities in both MOFs offered a platform to
decomposition of the framework. MOF 2 experiences a weight accomplish base-catalyzed reaction. Consequently, 1 and 2
loss of 13.58% before 324 °C, which can be attributed to the were used as heterogeneous catalysts to catalyze Knoevenagel
liberation of the water and DMF molecules in the pores of the condensation reactions between benzaldehyde derivatives and
framework (calculated value is 13.37%). Then the framework malononitrile. Before used as catalysts, 1 and 2 were activated
starts to collapse at 350 °C. The thermogravimetric analyses of by exchange and removal of the guest molecules in the channels.
1
a and 2a were also examined. As shown in Figure S6 and S7, The activated samples (1a and 2a) were employed in the typical
the frameworks of 1a and 2a have no obvious weight loss before procedure: benzaldehyde derivatives (1 mmol), malononitrile (2
35 °C and 337 °C respectively, which indicate that the mmol) and catalyst (1a or 2a) (0.02 mmol) were charged into 10
frameworks of 1a and 2a still remain even if the gust molecules mL round-bottomed flask and stirred at 60 °C under solvent-
3
are removed.
free condition. The reaction progress was monitored by thin
layer chromatography (TLC). The conversion rate of reaction
was determined directly by H NMR spectroscopy. Taking
Gas Adsorption
1
The structural rigidity and the big channels motivated us to
investigate the gas adsorptive performances of the two MOFs.
Before measurement, they were activated by methanol
exchanging 3 days and then degasing at 100 °C for 12 h to
remove the guest molecules. As shown in Figure S8, the two
MOFs have almost no uptake for N
the thiazole nitrogen and pendant −NH
pores in both MOFs, we investigated their adsorption
performances for CO . As shown in Figure 3, MOF 2 show type I
benzaldehyde for example, the relationship between the
conversion rate and the reaction time was examined. As shown
in Figure S11, the reaction conversion rate gradually increases
along with prolonged reaction time and the reaction is finished
completely in 6 h, indicating that 1a and 2a can be used as
effective catalysts for Knoevenagel condensation reaction
between benzaldehyde and malononitrile. So the reaction time
was fixed at 6 h when other benzaldehyde derivatives were
used in Knoevenagel reaction.
To investigate the substituent effect, several different
substituted benzaldehyde derivatives were employed in the
aforementioned reaction. As shown in Table 1, the nature of the
substituent on the benzene ring has a significant influence on
Knoevenagel condensation reaction. The electron-withdrawing
2
at 77 K. In consideration of
2
group functionalized
2
adsorption curves for CO
uptakes of 50 cm /g and 35 cm /g, which corresponds to
approximately 9.8 wt % (1.5 molecules/formula) and 6.9 wt %
2
at 195 K and 273 K with maximum
3
3
(
1 molecules/formula), respectively. Obviously, 2 can selectively
adsorb CO from CO /N mixture (Figure 3b), which is a
prerequisite for a CO
capture material.77,78 The enthalpy of
adsorption for CO was obtained to be 19.7 kJ/mol by the
Clausius–Clapeyron equation from the adsorption isotherm at
95 K and 273 K (Figure S9). This value is higher than the
enthalpy of liquefaction of CO (17 kJ/mol), indicating that the
thiazole nitrogen atom and pendant −NH group provide a
considerable improvement CO adsorption, which is
2
2
2
2
group (−NO
reaction (Yield more than 99%, Entries 4−7), whereas the
electron-donating group (−CH , −OCH ) is detrimental to the
2
, −CN, −Br) is beneficial to improve the yield of
2
3
3
1
conversion rate of reaction and the electron-donating ability is
inversely proportional to the yield of reaction (Yield less than 90%
for −CH and 70% for −OCH , Entries 2 and 3). Moreover, the
3 3
position of the substituent on the benzene ring has also obvious
impact on Knoevenagel condensation reaction. Benzaldehyde
2
2
2
with electron-withdrawing group (−NO
para-position shows an obviously higher yield (Entries 4−7)
3
while benzaldehyde with electron-donating group (−CH , −OCH )
2
, −CN, −Br) in ortho- or
3
in para-position reveals a relatively lower yield (Entries 2 and 3).
Meanwhile, the substituent situated at ortho-position or para-
position of the aldehyde group has more serious influence than
that at meta-position. Compared with para-position, −OCH
meta-position of the aldehyde group is beneficial for the
reaction (Entry 3 and 8). The reason should be that −OCH in
meta-position of the benzene ring behaves electron-
adsorption isotherms at withdrawing property to the whole benzaldehyde system,
7 K for 2. Filled and open symbols represent adsorption and consequently causing that aldehyde group in meta-position
3
in
3
Figure 3. (a) CO
adsorption isotherms at 273 K and N
7
2 2
adsorption isotherms at 195 K for 2. (b) CO
2
desorption, respectively.
shows higher reactivity. In addition, the amount of the
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Page 6 of 9
ARTICLE
Journal Name
2
groups and thiazole
substituent on the benzene has also some effect on from the synergistic effect of active −NH
Knoevenagel condensation reaction. The more benzaldehyde nitrogen atoms. Only in the specific strucDtOuIr:e10s.1o0f39M/CO9FDT10a03a9n1dF
contains the electron-donating group, the lower the yield of 2a, -NH and thiazole nitrogen can take effect synergistically
View Article Online
2
reaction is (Entries 9 and 10).
and maximize their catalytic activities.
Finally, to validate the recycling and stabilities of 1a and 2a,
their recyclable experiments were examined for five times
Table 1. Knoevenagel condensation reactions of the different
benzaldehyde derivatives catalyzed by 1a and 2a.
(Table S4). The catalyst can be easily isolated by centrifugation
CN
CN
CN
Catlyst (2 mol%)
and be reused in the next round catalytic experiment. The
reaction conversion rate is not obviously reduced after five
round catalytic experiments. Meanwhile, PXRD, IR as well as
SEM were applied to characterize the catalyst before and after
five round catalytic experiments. As shown in Figure S12, IR
spectra of 1a and 2a are nearly unchanged before and after the
catalytic reaction, indicating their good thermal and chemical
stabilities. As shown in Figure S13, PXRD patterns of 1a and 2a
agree well before and after the catalytic reaction, indicating
that their frameworks remain unchanged. As shown in Figure
S14, the morphologies of 1a and 2a remain unchanged before
and after the catalytic reaction. Therefore, 1a and 2a are stable
and recyclable heterogeneous catalysts for Knoevenagel
condensation reaction. To the best of our knowledge, only a few
MOFs have been reported as efficient catalysts for Knoevenagel
condensation reaction under solvent-free condition up to
CHO
+
R
CN
Solvent-free, 60 ℃, 6 h
R
Entry
1
Substrate
1a, Yield (%)
2a, Yield (%)
CHO
99.9
99.8
H3C
CHO
2
3
4
5
6
89
86
H3CO
O2N
NC
CHO
70
71
CHO
99.7
99.8
99.8
99.9
99.8
99.9
CHO
CHO
Br
8
0-82
now.
CHO
7
8
9
99.8
96
99.9
97
Br
Conclusions
CHO
In conclusion, two amino functionalized Zn/Cd-MOFs have been
successfully designed and synthesized by assembling the linkers
Py TTz and 2-NH -H BDC with the binuclear metal nodes. The
2 2 2
two MOFs possess similar 2-fold interpenetrated 3D bipillared-
layer framework structures. Moreover, the numerous thiazole
2
nitrogen atoms and pendant −NH groups are present in the
channels, coupled with the good chemical and high thermal
stability, endow the two MOFs good performances for gas
adsorption and catalyzing Knoevenagel condensation reaction.
The gas adsorption data show that MOF 2 have a moderate CO
uptake and good CO /N selectivity with potential for practical
separation of CO from CO /N mixture. Meanwhile, PXRD, IR as
well as SEM of the catalyst before and after the catalytic
reaction demonstrate that the two MOFs can efficiently
catalyze Knoevenagel condensation reaction as stable
recyclable heterogeneous catalyst under solvent-free condition.
To design and synthesize the multifunctional MOFs with more
superior performance, their specific active sites, intrinsic
structure-active relationships, and plausible catalytic
mechanism are underway.
H3CO
H3CO
H3C
CHO
65
65
H3C
CHO
1
0
72
68
H3C
To further validate the role of 2-NH
unit in MOFs for catalytic experiment, the control experiments
were performed with free ligand 2-NH -H BDC or Py TTz as
catalysts (Table S3). There is no product to be detected without
any catalyst. With 2-NH -H BDC as catalyst, the conversion rate
is negligible (around 1%). With Py TTz as catalyst, the
conversion rate is relatively higher (72%), which might benefit
from its partially homogeneous catalysis. With 2-NH -H BDC
and Py TTz as catalyst simultaneously, the conversion rate is
lower than that with Py TTz solely, which is caused by the
acidity of 2-NH -H BDC weakening the basicity of nitric
heterocyclic moiety. Additionally, to verify the catalytic active
site in Py TTz whether lying in pyridine unit or thiazolo[5,4-
d]thiazole unit, the control experiment was performed with 2,5-
Diphenylthiazolo[5,4-d]thiazole (Ph TTz) (without pyridine unit)
as catalyst (Entry 5 in Table S3). With Ph TTz as catalyst, the
conversion rate is 48%, which is lower than that with Py TTz,
indicating that both pyridine unit and thiazolo[5,4-d]thiazole
unit have some catalytic active in Py TTz. Comparing with high
-BDC2- unit and Py
TTz
2 2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
Conflicts of interest
2
There are no conflicts to declare.
2
2
Acknowledgements
2
catalytic activities of 1a and 2a, we speculate that catalytic
effect is not from the single ligand or the sum of ligands but
We are grateful for the financial aid from the National Natural
Science Foundation of China (No. 21371154, 21371153), the
6
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 9
Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Journal Name
ARTICLE
3
3
3
1 S.-Q. Lu, Y.-Y. Liu, Z.-M. Duan, Z.-X. Wang, M.-X.ViLeiwaAnrtdicleXO. nHlinee,
Program for Innovative Research Team (in Science and
Technology) in Universities of Henan Province (No.
Cryst. Growth Des., 2018, 18, 4602-4610.
DOI: 10.1039/C9DT00391F
2 J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang and C. Y. Su, Chem.
Soc. Rev., 2014, 43, 6011-6061.
3 J. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen and J.
T. Hupp, Chem. Soc. Rev., 2009, 38, 1450-1459.
1
9IRTSTHN022).
Notes and references
34 Y.-X. Tan, Y.-P. He, D. Yuan and J. Zhang, Applied Catalysis B:
Environmental, 2018, 221, 664-669.
1
2
W. P. Lustig and J. Li, Coord. Chem. Rev., 2018, 373, 116-147.
T. L. Easun, F. Moreau, Y. Yan, S. Yang and M. Schroder, Chem.
Soc. Rev., 2017, 46, 239-274.
3
3
3
3
3
5 E. X. Chen, M. Qiu, Y. F. Zhang, Y. S. Zhu, L. Y. Liu, Y. Y. Sun, X.
Bu, J. Zhang and Q. Lin, Adv. Mater., 2018, 30, 1704388.
6 C. Yu, Z. Shao and H. Hou, Chemical Science, 2017, 8, 7611-
3
4
5
6
7
8
9
1
G. Maurin, C. Serre, A. Cooper and G. Ferey, Chem. Soc. Rev.,
7
619.
2
017, 46, 3104-3107.
7 Z. Shao, C. Huang, J. Dang, Q. Wu, Y. Liu, J. Ding and H. Hou,
Chem. Mater., 2018, 30, 7979-7987.
Y. Bai, Y. Dou, L. H. Xie, W. Rutledge, J. R. Li and H. C. Zhou,
Chem. Soc. Rev., 2016, 45, 2327-2367.
8 T. He, Y.-Z. Zhang, X.-J. Kong, X.-L. Lv, L.-H. Xie and J.-R. Li,
Crystal Growth & Design, 2019, 19, 430-436.
9 Z. Shao, M. Liu, J. Dang, C. Huang, W. Xu, J. Wu and H. Hou,
Inorg. Chem., 2018, 57, 10224-10231.
0 D. W. Keith, Science, 2009, 325, 1654-1655.
1 G. T. Rochelle, Science, 2009, 325, 1652-1654.
2 J.-Q. Liu, G.-P. Li, W.-C. Liu, Q.-L. Li, B.-H. Li, R. W. Gable, L. Hou
and S. R. Batten, ChemPlusChem, 2016, 81, 1299-1304.
3 K. Zhou, S. Chaemchuen and F. Verpoort, Renewable and
Sustainable Energy Reviews, 2017, 79, 1414-1441.
C. Wang, X. Liu, N. Keser Demir, J. P. Chen and K. Li, Chem. Soc.
Rev., 2016, 45, 5107-5134.
X. Zhao, Y. Wang, D. S. Li, X. Bu and P. Feng, Adv. Mater., 2018,
3
0, 1705189.
4
4
4
M. I. Nandasiri, S. R. Jambovane, B. P. McGrail, H. T. Schaef
and S. K. Nune, Coord. Chem. Rev., 2016, 311, 38-52.
Z. Bao, G. Chang, H. Xing, R. Krishna, Q. Ren and B. Chen,
Energy Environ. Sci., 2016, 9, 3561–3796.
4
Y. He, W. Zhou, R. Krishna and B. Chen, Chem. Commun., 2012,
4
8, 11813-11831.
4
4
4 D. Aaron and C. Tsouris, Sep. Sci. Technol., 2005, 40, 321-348.
5 A. J. Emerson, C. S. Hawes, M. Marshall, G. P. Knowles, A. L.
Chaffee, S. R. Batten and D. R. Turner, Chem. Mater., 2018, 30,
0 J. R. Li, J. Sculley and H. C. Zhou, Chem. Rev., 2012, 112, 869-
9
32.
1
1
1 H. Wang and J. Li, Dalton Trans., 2018, 47, 4027-4031.
6
614-6618.
6 Z. Zhang, Y. Zhao, Q. Gong, Z. Li and J. Li, Chem. Commun.,
013, 49, 653-661.
2 H. R. Fu, F. Wang and J. Zhang, Dalton Trans., 2015, 44, 2893-
4
4
4
4
5
2
896.
2
1
1
1
3 W. P. Lustig, S. Mukherjee, N. D. Rudd, A. V. Desai, J. Li and S.
K. Ghosh, Chem. Soc. Rev., 2017, 46, 3242-3285.
4 R.-W. Huang, Y.-S. Wei, X.-Y. Dong, X.-H. Wu, C.-X. Du, S.-Q.
Zang and T. C. W. Mak, Nat. Chem., 2017, 9, 689-697.
7 R. Vaidhyanathan, S. S. Iremonger, G. K. H. Shimizu, P. G. Boyd,
S. Alavi and T. K. Woo, Science, 2010, 330, 650-653.
8 R. Banerjee, A. Phan, B. Wang, C. Knobler, H. Furukawa, M.
O'Keeffe and O. M. Yaghi, Science, 2008, 319, 939-943.
9 Q. Q. Zhang, X. F. Liu, L. Ma, Y. S. Wei, Z. Y. Wang, H. Xu and S.
Q. Zang, Chem. Commun., 2018, 54, 12029-12032.
5 D. Masih, V. Chernikova, O. Shekhah, M. Eddaoudi and O. F.
Mohammed, ACS Appl. Mater. Interfaces, 2018, 10, 11399-
1
1405.
0 R. W. Flaig, T. M. Osborn Popp, A. M. Fracaroli, E. A. Kapustin,
M. J. Kalmutzki, R. M. Altamimi, F. Fathieh, J. A. Reimer and O.
M. Yaghi, J. Am. Chem. Soc., 2017, 139, 12125-12128.
1
1
1
1
2
2
2
2
2
2
2
2
6 L. Zhai, Z.-X. Yang, W.-W. Zhang, J.-L. Zuo and X.-M. Ren, J.
Mater. Chem. C, 2018, 6, 7030-7041.
7 F.-M. Wang, L. Zhou, W. P. Lustig, Z. Hu, J.-F. Li, B.-X. Hu, L.-Z.
Chen and J. Li, Cryst. Growth Des., 2018, 18, 5166-5173.
8 B. L. Martinez, A. D. Shrode, R. J. Staples and R. L. LaDuca,
Polyhedron, 2018, 151, 369-380.
9 S.-R. Zhang, J. Li, D.-Y. Du, J.-S. Qin, S.-L. Li, W.-W. He, Z.-M. Su
and Y.-Q. Lan, J. Mater. Chem. A, 2015, 3, 23426-23434.
0 W. Xie, W. W. He, S. L. Li, K. Z. Shao, Z. M. Su and Y. Q. Lan,
Chem. Eur. J., 2016, 22, 17298-17304.
5
5
5
1 H. C. Kim, S. Huh, D. N. Lee and Y. Kim, Dalton Trans., 2018,
4
7, 4820-4826.
2 W.-S. Kim, K. Y. Lee, E.-H. Ryu, J.-M. Gu, Y. Kim, S. J. Lee and S.
Huh, Eur. J. Inorg. Chem., 2013, 2013, 4228-4233.
3 K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. D.
Bloch, Z. R. Herm, T. H. Bae and J. R. Long, Chem. Rev., 2012,
1
12, 724-781.
5
5
5
5
5
4 W. Lu, J. P. Sculley, D. Yuan, R. Krishna, Z. Wei and H. C. Zhou,
Angew. Chem. Int. Ed., 2012, 51, 7480-7484.
1 D. Masih, S. M. Aly, E. Alarousu and O. F. Mohammed, J.
Mater. Chem. A, 2015, 3, 6733-6738.
5 T. M. McDonald, W. R. Lee, J. A. Mason, B. M. Wiers, C. S. Hong
and J. R. Long, J. Am. Chem. Soc., 2012, 134, 7056-7065.
6 T. M. McDonald, D. M. D'Alessandro, R. Krishna and J. R. Long,
Chem. Sci., 2011, 2, 2022-2028.
2 C. L. White and R. L. LaDuca, Inorg. Chim. Acta, 2016, 441, 169-
1
80.
3 L. H. Cao, F. Shi, W. M. Zhang, S. Q. Zang and T. C. W. Mak,
Chem. Eur. J., 2015, 21, 15705-15712.
7 S. Singh Dhankhar, N. Sharma, S. Kumar, T. J. Dhilip Kumar and
C. M. Nagaraja, Chem. Eur. J., 2017, 23, 16204-16212.
8 R. Haldar, S. K. Reddy, V. M. Suresh, S. Mohapatra, S.
Balasubramanian and T. K. Maji, Chem. Eur. J., 2014, 20, 4347-
4 V. Stavila, A. A. Talin and M. D. Allendorf, Chem. Soc. Rev.,
2
014, 43, 5994-6010.
5 H. Y. Li, H. Xu, S. Q. Zang and T. C. W. Mak, Chem. Commun.,
016, 52, 525-528.
2
4
356.
6 H.-Y. Li, Y.-L. Wei, X.-Y. Dong, S.-Q. Zang and T. C. W. Mak,
Chem. Mater., 2015, 27, 1327-1331.
5
6
6
6
9 S. Hasegawa, S. Horike, R. Matsuda, S. Furukawa, K.
Mochizuki, Y. Kinoshita and S. Kitagawa, J. Am. Chem. Soc.,
7 N. S. Bobbitt, M. L. Mendonca, A. J. Howarth, T. Islamoglu, J.
T. Hupp, O. K. Farha and R. Q. Snurr, Chem. Soc. Rev., 2017,
2
007, 129, 2607-2614.
0 Y. K. Hwang, D. Y. Hong, J. S. Chang, S. H. Jhung, Y. K. Seo, J.
Kim, A. Vimont, M. Daturi, C. Serre and G. Ferey, Angew.
Chem. Int. Ed., 2008, 47, 4144-4148.
4
6, 3357-3385.
2
2
3
8 S. Y. Jiang, W. W. He, S. L. Li, Z. M. Su and Y. Q. Lan, Inorg.
Chem., 2018, 57, 6118-6123.
9 D. Xie, Y. Ma, Y. Gu, H. Zhou, H. Zhang, G. Wang, Y. Zhang and
H. Zhao, J. Mater. Chem. A, 2017, 5, 23794-23804.
0 J. S. Qin, S. R. Zhang, D. Y. Du, P. Shen, S. J. Bao, Y. Q. Lan and
Z. M. Su, Chem. Eur. J., 2014, 20, 5625-5630.
1 J. Park, J. R. Li, Y. P. Chen, J. Yu, A. A. Yakovenko, Z. U. Wang,
L. B. Sun, P. B. Balbuena and H. C. Zhou, Chem. Commun.,
2
012, 48, 9995-9997.
2 Y. Luan, Y. Qi, H. Gao, R. S. Andriamitantsoa, N. Zheng and G.
Wang, J. Mater. Chem. A, 2015, 3, 17320-17331.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Page 8 of 9
ARTICLE
Journal Name
6
6
6
6
6
3 B. Parmar, P. Patel, V. Murali, Y. Rachuri, R. I. Kureshy, N.-u. H. 73 G. M. Sheldrick, Acta Crystallogr., Sect. A: FoundV.ieCwrAyrstitcalellOonglirn.e,
Khan and E. Suresh, Inorg. Chem. Front., 2018, 5, 2630-2640. 2008, 64, 112-122.
4 U. P. N. Tran, K. K. A. Le and N. T. S. Phan, ACS Catal., 2011, 1, 74 O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and
20-127. H. Puschmann, J. Appl. Crystallogr., 2009, 42, 339-341.
5 L. Shi, T. Wang, H. Zhang, K. Chang, X. Meng, H. Liu and J. Ye, 75 G. M. Sheldrick, Acta Crystallogr., Sect. C: Struct. Chem., 2015,
Adv. Sci., 2015, 2, 1500006. 71, 3-8.
6 P. Serra-Crespo, E. V. Ramos-Fernandez, J. Gascon and F. 76 P. van der Sluis and A. L. Spek, Acta Crystallogr., Sect. A:
Kapteijn, Chem. Mater., 2011, 23, 2565-2572. Found. Crystallogr., 1990, 46, 194-201.
7 X. Si, C. Jiao, F. Li, J. Zhang, S. Wang, S. Liu, Z. Li, L. Sun, F. Xu, 77 A. Demessence, D. M. D’Alessandro, M. L. Foo and J. R. Long,
DOI: 10.1039/C9DT00391F
1
Z. Gabelica and C. Schick, Energy Environ. Sci., 2011, 4, 4522-
527.
8 L. Ma, X. Wang, D. Deng, F. Luo, B. Ji and J. Zhang, J. Mater.
Chem. A, 2015, 3, 20210-20217.
9 Z.-W. Zhai, S.-H. Yang, M. Cao, L.-K. Li, C.-X. Du and S.-Q. Zang,
Cryst. Growth Des., 2018, 18, 7173-7182.
0 A. N. Woodward, J. M. Kolesar, S. R. Hall, N. A. Saleh, D. S. 80 C. Yao, S. Zhou, X. Kang, Y. Zhao, R. Yan, Y. Zhang and L. Wen,
J. Am. Chem. Soc., 2009, 131, 8784-8786.
78 W.-H. Xing, H.-Y. Li, X.-Y. Dong and S.-Q. Zang, J. Mater. Chem.
A, 2018, 6, 7724-7730.
79 J.-R. Li, Y. Ma, M. C. McCarthy, J. Sculley, J. Yu, H.-K. Jeong, P.
B. Balbuena and H.-C. Zhou, Coord. Chem. Rev., 2011, 255,
1791-1823.
4
6
6
7
Jones and M. G. Walter, J. Am. Chem. Soc., 2017, 139, 8467-
473.
1 D. Li, Z. Zhang, S. Zhao, Y. Wang and H. Zhang, Dalton Trans.,
Inorg. Chem., 2018, 57, 11157-11164.
8
81 X. S. Wang, J. Liang, L. Li, Z. J. Lin, P. P. Bag, S. Y. Gao, Y. B.
Huang and R. Cao, Inorg. Chem., 2016, 55, 2641-2649.
82 L.-C. Lee, J. Lu, M. Weck and C. W. Jones, ACS Catal., 2016, 6,
784-787.
7
7
2
011, 40, 1279-1285.
2 CrysAlisPro
Technologies.
2012,
Version
1.171.136.131;
Agilent
8
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 9 of 9
Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
View Article Online
DOI: 10.1039/C9DT00391F
Journal Name
ARTICLE
Table of Content
Two amino functionalized Zn/Cd-MOFs can be employed to adsorb CO
solvent-free condition.
2
selectively and to catalyze Knoevenagel reaction under
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
Please do not adjust margins