Synthesis, characterization, crystal structure of magnesium compound based 3, 3′, 5, 5′-azobenzentetracarboxylic acid and application as high-performance heterogeneous catalyst for cyanosilylation

Article abstract of DOI:10.1016/j.molstruc.2016.12.005

A novel coordination compound with the formula {[H₃O]₂[Mg(ABTC)(DMI)₂]}_n (1) (H₄ABTC?=?3,3′,5,5′-azobenzene-tetracarboxylic acid, DMI?=?1,3-dimethy-2-imidazolidinone) as synthesized under solvothermal

Full text of DOI:10.1016/j.molstruc.2016.12.005

Accepted Manuscript
Synthesis, characterization, crystal structure of magnesium compound based 3, 3′, 5,
5′-azobenzentetracarboxylic acid and application as high-performance heterogeneous
catalyst for cyanosilylation
Yong-Peng Li, Ling-Juan Zhang, Wen-Juan Ji
PII:
S0022-2860(16)31295-9
10.1016/j.molstruc.2016.12.005
MOLSTR 23203
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 13 August 2016
Revised Date: 1 December 2016
Accepted Date: 2 December 2016
Please cite this article as: Y.-P. Li, L.-J. Zhang, W.-J. Ji, Synthesis, characterization, crystal structure
of magnesium compound based 3, 3′, 5, 5′-azobenzentetracarboxylic acid and application as high-
performance heterogeneous catalyst for cyanosilylation, Journal of Molecular Structure (2017), doi:
10.1016/j.molstruc.2016.12.005.
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Synthesis, characterization, crystal structure of Magnesium compound based
3, 3', 5, 5'-azobenzentetracarboxylic acid and application as high-performance
heterogeneous catalyst for cyanosilylation
Yong-Peng Li, Ling-Juan Zhang, Wen-Juan Ji*
Department of Chemistry & Material Science, Shanxi Normal University,
Gongyuan Str. 1, Linfen 041004, Shanxi Province, P. R. China;
Abstract: A novel coordination compound with the formula {[H3O]2[Mg(ABTC)(DMI)2]}n (1)
(H4ABTC = 3,3’,5,5’-azobenzene-tetracarboxylic acid, DMI = 1,3-dimethy-2-imidazolidinone) as
synthesized under solvothermal condition and characterized by thermogravimetric analysis, IR
spectroscopy, X-ray powder diffraction and single crystal X-ray diffraction. Compound 1 features
a novel 3-D anionic framework [Mg(ABTC)(DMI)2]n2n- constructed by linking adjacent 2-D layer
with the phenyl rings of the ABTC4- ligands and can be classified as a (4,4)-connected PtS porous
net; it also has highly heterogeneous catalysis activity for the cyanosilylation of carbonyl
compounds at low loading (0.1 mol%) leading to up to 99% conversion of benzaldehyde under
solvent-free conditions. When Mg-abtc MOF (1) was recycled five times, its catalytic activity
remained with an inconspicuous decrease.
Keywords: Metal-organic framework; Magnesium; Azo-group; Cyanosilylation; Heterogeneous
catalyst.
1. Introduction
In the past few years, carbonyl compounds have been the popular solution in preparation of
fine chemicals and pharmaceuticals[1-4]. However, it should be noted that the forming of the
C–C bond of these compounds are usually realized by the existence of homogeneous catalysts,
which are difficult to separate and recycle[5-6]. Therefore, it is important to find an efficient
heterogeneous catalysts in this organic sythesis process.
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*Corresponding author Email: ji18629288564@163.com

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Metal-organic frameworks (MOFs) are a class of permanently porous and crystalline
solid-state materials [7,8], that have recently shown remarkable potential as adsorbents and
catalysts [9-13] due to their large surface area, permanent porosity, high dispersed metal centers,
and tunable chemical pores [14-19]. Given these attributes, MOFs are well suited for the new
candidates as homogeneous or heterogeneous catalysts [20,21]. To date, various effective
strategies have been reported which are mainly based on the unsaturated metal centers in the
MOFs structure [22-25]. However, most of the open metal sites in MOFs easily coordinate with
solvent molecules, resulting in the decreased of catalytic performance. Few efforts have been paid
to exploring the organic ligands of MOFs as the catalytic center [26,27]. The development of a
new MOF, where the organic ligand acts as an efficient catalytic center has great potential for
heterogeneous catalysis [28-32].
Introducing a 3,3’,5,5’-azobenzene-tetracarboxylic acid (H4ABTC), as one type of bridging
aromatic tetracarboxylate organic ligand, possesses many advantages to design
catalytically-active MOFs [33,34]. (a) The exposed azo bond is from a well-known Lewis base
group, that is expected to modulate the catalytic performance. (b) The rigid H4abtc ligand has
four carboxyl group, which is then easily deprotonated to form various geometries. In these
geometries, multiple strong metal-oxygen coordination bonds can greatly enhance thermal
stability and rigidity of the framework [35-38]. we chose H4abtc as the organic linkers to
elaborate new MOFs, namely the {(H3O)2[Mg(ABTC)(DMI)2]}n (1) polymer. The single-crystal
X-ray analysis showed that the Mg2+ centers are coordinated to the ABTC4− linkers, thus forming
the “PtS”-type topological 3D network with the ligands with exposed azo-groups as pore walls.
From these results, compound 1 can be utilized to test as a Lewis base catalyst for carbon-carbon
(C–C) bond-forming reactions. Compound 1 shows high efficient as a heterogeneous catalyst for
cyanosilylation of various carbonyl group compounds under solvent-free conditions[24].
2. Experimental
2.1. Materials and measurements information
All chemicals used in this were analytically pure as-provided by commercial sources and used
without further purification. Elemental analysis (C, H, N) were carried out on a Vario EL-II
analyzer. The infrared spectra (KBr pellets) were recorded in the range 400–4000 cm−1 on a

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Perkin Elmer Spectrum BX FTIR spectrometer. The thermal stability of compound 1 were
recorded under an N2 atmosphere using SETARAM LABSYS equipment at a heating rate of
10 °C min−1. The Powder X-ray diffraction (PXRD) and the temperature dependent PXRD data
of 1 were collected on a Rigaku Ultima IV diffractometer (Cu radiation, λ=1.54056 Å). The
reaction conversions of heterogeneous catalytic were recorded by gas chromatography GC
analysis (FID from AGILENT 7820). The heterogeneous catalytic procedure involved adding 1.4
mg of dried compound 1 catalyst to a mixture of the corresponding 2.0 mmol for carbonyl
compound and 4.0 mmol for trimethylsilylcyanide (TMSCN) under a N2 atmosphere and
stirring the mixture at room temperature. The reaction was monitored by GC using a cross-linked
(95%)-dimethyl-(5%)-diphenylpolysiloxane column (HP-5, 30 m×0.32 mm×0.25 ꢀm), He
atmosphere, injector at 250℃, detector at 300℃, and oven temperature program of 15℃·min-1.
For filtration test, catalyst was separated after a reaction time of 30 min with 53.4 % conversion.
The reaction proceeded in the filtrate with no additional conversion after 6 hours.
2.2. Synthesis of {[H3O]2[Mg(ABTC)(DMI)2]}n (1)
A mixture of Mg(NO3)2﹒6H2O (30 mg, 0.1 mmol) with H4abtc (18 mg, 0.05 mmol) , DMI (5
mL), EtOH (2 mL) and H2O (1 mL) were placed in a 20 mL glass vial and heated at 110℃ for 7
days. After the mixture had been slowly cooled to room temperature, orange needle crystals were
obtained about 58% yield based on H4ABTC. Anal. Calcd for C26MgN6O12H32: C, 48.42; H,
5.00;N, 13. 03. Found: C, 48.88; H, 4.86; N, 13.15%. IR cm−1(KBr): 3451(s), 3124(s), 2351(w),
1635(s), 1398(s), 1125 (s), 980(w), 861(w), 743(w).
2.3. X-ray crystallography
Single-crystal X-ray analysis was collected using an Agilent Gemini EOS diffractometer
graphite-monochromated Mo-Kα radiation (λ = 0.71073 Å) at 298K[22]. The program of
CrysAlisPro was used for absorption correction. The structure of compound 1 was solved by
direct methods, and was refined by SHELXL-97 software of full-matrix least-squares [39]. All
non-hydrogen atoms in the framework of 1 were anisotropically[22]. Hydrogen atoms of the
organic H4ABTC ligand were generated on the specific carbon atomic sites, then refined
isotropically with fixed thermal factors. The SQUEEZE routine was used to treat the disordered

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solvent area and remove its contribution from the overall intensity data[39]. The lattice H3O+
molecules for compound 1 were deduced from elemental and TG analysis. This supplement was
added to the experimental section 2.3. The bond lengths and bond angles of 1 are described in
Table 1. Details for structural analysis and refinements were summarized in Table 2.
3. Results and discussion
3.1. Crystal structure description
X-ray crystallographic data reveal that 1 crystallizes in C2/c space group. The X-ray results also
2n-
indicate a 3-D anionic framework [Mg(ABTC)(DMI)2]n (Figure 1). The asymmetric unit of 1
contains one crystallographically unique Mg2+ ion, half H4abtc ligands and one DMI molecule.
We also observed a Mg(1) with slightly distorted octahedral coordination geometry is
six-coordinated by four carboxylate O atoms (O1, O1a, O4c, and O4b) from four ABTC4− groups,
two O atoms (O5 and O5a) from two coordinated DMI molecules (Figure 2). The Mg-O distances
range from 2.064 (2) to 2.105 (2) Å. The O-Mg-O bond angles ranged from 84.05 (7) to 176.50
(11) Å. The ABTC4- ligand has central symmetry able to link the four Mg atoms (Figure 3).The
Mg subunits are connected only by carboxylate oxygen atoms to form a 2-D (4, 4) layer in the
a,b-plane (Figure 4).
Adjacent layers linked by the phenyl rings from ligands along the c-axis direction to produce a
novel three dimensional (3D) anionic MOF (Figure 5). The solvent-accessible volume with 11.4%
total accessible volume was calculated using the PLATON routine[40]. In addition, the presence
of weak intermolecular interactions between adjacent coordinated DMI molecules inside the
channel enhanced the stability of the 3D framework. In addition, the presence of weak
intermolecular interactions between adjacent coordinated DMI molecules inside the channel
2n-
enhances the stability of the 3D framework. To classify the network topology of [Mg(ABTC)]n
in 1, we defined the organic linker abtc4- units and Mg ions acting as 4- and 4-connected nodes,
respectively. The two types of nodes link a unique 3-D 4,4-connected PtS porous framework
(Figure 6).
3.2. IR spectra, Thermal behaviors and powder X-ray diffraction
Figure 7 shows the FTIR spectra of sample 1 and that of the vacuum at 100 ℃ for 12 h . The
strong bands at 3451 cm-1 can be assigned to the carboxylate O-H group from the ABTC4− group.

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The absorptions observed at 1635 cm-1 was caused by the N=N of the ligand. The peaks at 1398
cm-1 and 743 cm-1 attributed to the C-H and -CH2-CH2- of the DMI, respectively [41,42]. The
spectra of active sample 1 match very closely apart from some intensity changes. The spectra of 1
and the dried sample clearly suggests the presence of coordinated DMI molecules in 1 and the
active sample.
The thermal stability of 1 was investigated by TGA in the 30−800°C range in a nitrogen
environment. As shown in Figure 8, the initial weight loss of 1 was about 5.1% (calcd. 5.6%) in
the temperature range of 25-170 corresponding to the removal of lattice water molecules,
weight loss of 26.5% (calcd. 26.8%) ranging from 170-315 is consistent with the removal of
coordinated DMI molecules, followed by weight loss in the 315-460 corresponds to the
decomposition of the compound 1. The 3D framework has fairly high thermal stability (305℃)
among all the reported MOFs [43-49] based on the ABTC4- information shown in Table 3.
As shown in Figure 9, the temperature dependent PXRD experiments for 1 30-330℃ suggested
that water molecules removed around 100-170℃, while decomposition starts at around 310℃.
These results are in accordance with the TGA analyses.
3.3. The heterogeneous catalytic cyanosilylation with Mg-MOF 1
We investigated the cyanosilylation of carbonyl compounds to test the catalytic activity of 1.
Benzaldehyde was initially used as a model substrate; a loading of 0.1 mol% of 1 led to a 99.8%
conversion in the absence of solvent. Further experiments showed that various carbonyl
compounds with electron-rich aromatic groups (entries 1-4), phenyl (entry 5), and hetero aromatic
group (entry 6) yield corresponding products via favorable conversions. Aliphatic aldehydes
(entry 7) and ketones (entries 8-9) also reacted with Trimethylsilyl (TMSCN) to corresponding
products with high yields (Table 4, 5). The position of the substituent on the aromatic ring did not
significantly affect the substrate conversion (entries 1-2). The effective conversions of carbonyl
compounds suggest that the exposed azo-centers of ligands can act as efficient Lewis base sites
for cyanosilylation. Further, both the medium conversion of bulky 9-anthracenecarboxaldehyde
(entry 4) and low porosity of the MOF skeleton indicate that catalytic activity is strongly
dependent on the surface area of catalyst 1. To confirm that the catalysis was indeed
heterogeneous, we confirmed that removal of 1 by filtration after 30 min completely shut down

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the reaction, this produced 53.4% total conversion upon maintaining 6 hours. This indicates that
no homogeneous catalyst species existed in the reaction solution[24].
3.3.1 Recycle experiments
A reused experiment was carried out the cyanosilylation of benzaldehyde[24]. The reaction
was carried out under standard conditions, the catalyst was recovered by filtration, washed with
ethanol, and vacuum for 12 h prior to reuse. The catalyst was easily separated from the reaction
solution via centrifugation and washed with ethanol, dried at 100 under vacuum for 12 hours for
catalysis[22]. The stable heterogeneous catalyst 1 was able to be reused up to five times without
any obvious loss of activity (Figure 10). The stability of compound 1 was examined after the
catalytic study by PXRD; we obtained the same PXRD patterns as the as-synthesized phase,
indicating that the compound was stable.
4. Conclusion
In this study, we successfully synthesized a high-thermal-stability, porous Mg-abtc MOF 1.
Compound 1 showed porous walls with exposed azo-groups, acting as a Lewis base catalyst for
the cyanosilylation of carbonyl compounds under solvent-free conditions[24]. The heterogeneous
catalyst can be reused up to five times without any significant loss of activity.
Supplementary materials
Crystallographic data have been deposited in the Cambridge Crystallographic Data Center under
the CCDC number: CCDC 1444979, that contains the supplementary crystallographic data for
this paper. The data can be obtained free of charge via the web application at
www.ccdc.cam.ac.uk/conts/retrieving.html.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported the National Natural Science Foundation for youths of China [grant
number 21601115 and 21402112]; High School Science and Technology Innovation Projects of
ShanXi Province Education Department [grant number 2015156]; Natural Science Foundation of
shanxi normal university[grant number ZR1406]; and Graduate Student Innovation Fund project

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of Shanxi Province [grant number 03010031] which are gratefully acknowledged.
References
[1] X. N. Zhang, L. Liu, Z. B. Han, M. L. Gao, D. Q. Yuan, A dual-function Cd (II) -organic-framework
demonstrating selective sensing of Zn2+ and Fe3+ ions exclusively and size-selective catalysis towards
cyanosilylation. RSC. Adv. 5 (2015), pp. 10119–10124.
[2] S. Martin, R. Porcar, E. Peris, M.I. Burguete, E. Garcia-Verdugo, S.V. Luis. Supported ionic liquid-like phases
as organocatalysts for the solvent-free cancellation of carbonyl compounds: from batch to continuous flow
process. Green Chem.16 (2014), pp. 1639–1647.
[3] G. Wang, L. Wang, X. Fei, Y. Zhou, R. F. Sabirianov, W. N. Mei, C. L. Cheung, Probing the bifunctional
catalytic activity of ceria nanorods towards the cyanosilylation reaction. Cata. Sci. Technol. 3 (2013), pp.
2602–2609.
[4] L. Zhang, J. Cheng, T. Ohishi, Z. Hou, Copper-Catalyzed Direct Carboxylation of C-H Bonds with Carbon
Dioxide. Angew. Chem. Int. Ed. 49 (2010), pp. 8670 –867.
[5] W. Xu, Y. Li, B. Yu, J. Yang, Y. Zhang, X. Chen, G. Zhang, , Z. Gao, Ligand-tailored single-site silica
supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction. J. Solid. State.
Chem. 221 (2015), pp. 208–215.
[6] B. Li, K. Leng, Y. Zhang, J. J. Dines, J. Wang, Y. Hu, D. Ma, Z. Shi, L. Zhu, D. Zhang, Y. Sun, Metal–Organic
Framework Based upon the Synergy of a Brønsted Acid Framework and Lewis Acid Centers as a Highly
Efficient Heterogeneous Catalyst for Fixed-Bed Reactions. J. Am. Chem. Soc. 137 (2015), pp. 4243–4248.
[7] Q. L. Zhu, Q. Xu, Metal-organic framework composites. Chem. Soc. Rev. 43 (2014), pp. 5468–5512.
[8] H. C. Zhou, J.R. Long, O.M. Yaghi, Introduction to Metal–Organic Frameworks. Chem. Rev. 112 (2012), pp.
673–674.
[9] Y. E. Cheon, J. Park, M.P. Suh, Selective gas adsorption in a magnesium-based metal-organic framework.
Chem. Commun. 36 (2009), pp. 5436–5438.
[10] S. Yang, X. Lin, A. J. Blake, K. M. Thomas, P. Hubberstey, N. R. Champness, M. Schroder, Enhancement of
H2 adsorption in Li+-exchanged coordination framework materials. Chem. Commun. 46 (2008), pp.
6108–6110.
[11] Q. G. Zhai, N. Bay, S. n. Li, X. Bu, P. Feng, Design of Pore Size and Functionality in Pillar-Layered
Zn-Triazolate-Dicarboxylate Frameworks and Their High CO2/CH4 and C2 Hydrocarbons/CH4 Selectivity.

ACCEPTED MANUSCRIPT
Inorg. Chem. 54 (2015), pp. 9862–9868.
[12] J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang, C. Y. Su, Applications of metal–organic frameworks in
heterogeneous supramolecular catalysis. Chem. Soc. Rev. 43 (2014), pp. 6011–6061.
[13] S. Q. Chen, Q. G. Zhai, S. N. Li, Y. C. Jiang, M. C. Hu, Channel Partition into Nanoscale Polyhedral Cages
of a Triple-Self-Interpenetrated Metal–Organic Framework with High CO2 Uptake. Inorg. Chem. 54 (2015),
pp. 10–12.
[14] J. C. Wang, F. W. Ding, J. P. Ma, Q. K. Liu, J. Y. Cheng, Y. B. Dong, Co (II) -MOF: A Highly Efficient
Organic Oxidation Catalyst with Open Metal Sites. Inorg. Chem. 54 (2015), pp. 10865–10872.
[15] J. M. Brunel, I. P. Holmes, Chemically Catalyzed Asymmetric Cyanohydrin Syntheses.Angew. Chem. Int. Ed.
43(2004), pp. 2752–2778.
[16] K. Schlichte, T. Kratzke, S. Kaskel. Improved synthesis, thermal stability and catalytic properties of the
metal-organic framework compound Cu3 (BTC) . Microporous & Mesoporous Materials. 73 (2004), pp.
2
81–88.
[17] S. Ou, C. D. Wu, Rational construction of metal-organic frameworks for heterogeneous catalysis.Inorg.
Chem. Front. 1 (2014), pp. 721–734.
[18] J. Xia, J. Xu, Y. Fan, T. Song, L. Wang, J. Zheng, Indium Metal–Organic Frameworks as High-Performance
Heterogeneous Catalysts for the Synthesis of Amino Acid Derivatives. Inorg. Chem. 53 (2014), pp.
10024–10026.
[19] S. Hasegawa, S. Horike, R. Matsuda, S. Furukawa, K. Mochizuki, Y. Kinoshita, S. Kitagawa,
Three-Dimensional Porous Coordination Polymer Functionalized with Amide Groups Based on Tridentate
Ligand:ꢁ Selective Sorption and Catalysis. J. Am. Chem. Soc. 129 (2007), pp. 2607–2614.
[20] J. Gascon, A. Corma, F. Kapteijn, F. X. Llabrés I Xamena, Metal Organic Framework Catalysis: Quo Vadis?
ACS Catal. 4 (2014), pp. 361–378.
[21] R. K. Das, A. Aijaz, M. K. Sharma, P. Lama, P. K. Bharadwaj, Direct Crystallographic Observation of
Catalytic Reactions inside the Pores of a Flexible Coordination Polymer. Chem.Eur. J. 18 (2012), pp.
6866–6872.
[22] X. Cui, M. C. Xu, L. J. Zhang, R. X. Yao, X. M. Zhang, Solvent-free heterogeneous catalysis for
cyanosilylation in a dynamic cobalt-MOF. Dalton Trans. 44 (2015), pp. 12711–12716.
[23] D. Kumar, M. S. Mashuta, C. A.Grapperhaus, Metal-centered oxidation decreases nitrile hydration activity of

ACCEPTED MANUSCRIPT
bioinspired (N2S3)Ru-PPh3 precatalysts. Inorg. Chem. Commun. 61 (2015), pp. 197–199.
[24] L. J. Zhang, C. Y. Han, Q. Q. Dang, Y. H. Wang, X. M. Zhang, Solvent-free heterogeneous catalysis for
cyanosilylation in a modified Sodalite-type Cu (II) -MOF. RSC Adv. 5 (2015), pp. 24293–24298.
[25] P. D. C. Dietzel, P. A. Georgiev, J. Eckert, R. Blom, T. Strassle, T. Unruh, Interaction of hydrogen with
accessible metal sites in the metal-organic frameworks M2 (dhtp) (CPO-27-M; M = Ni, Co, Mg). Chem.
Commun. 46 (2010), pp. 4962–4964.
[26] P. V. Dau, S. M. Cohen, Site-Isolated Metal–Organic Framework-Based Tandem Catalyst. Inorg. Chem. 54
(2015), pp. 3134–3138.
[27] S. Roy, C.B. George, M. A. Ratner, Catalysis by a Zinc-Porphyrin-Based Metal–Organic Framework: From
Theory to Computational Design. J. Phys. Chem. C. 116 (2012), pp. 23494–23502.
[28] K. Mo, Y. Yang, Y. Cui, A Homochiral Metal–Organic Framework as an Effective Asymmetric Catalyst for
Cyanohydrin Synthesis. J. Am. Chem. Soc. 136 (2014), pp. 1746–1749.
[29] Y. Jin, Multifunctional Compact Hybrid Au Nanoshells: A New Generation of Nanoplasmonic Probes for
Biosensing, Imaging, and Controlled Release. Acc. Chem. Res. 47 (2014), pp. 138–148.
[30] F. Xing, J. Jia, L. Liu, L. Zhong, M. Shao, Y. l. Bai, Y. Zhao, S. Zhu, X. He, M. Li, Synthesis, structure and
adsorption of coordination polymers constructed from 3,3 [prime or minute], 5,5 [prime or minute]
-azobenzenetetracarboxylic acid and Zn ions. CrystEngComm. 15 (2013), pp. 4970–4980.
[31] M. Meng, D. C. Zhong, T. B. Lu, Three porous metal-organic frameworks based on an
azobenzenetricarboxylate ligand: synthesis, structures, and magnetic properties.CrystEngComm. 13 (2011),
pp. 6794–6800.
[32] D. S. Li, X. J. Ke, J. Zhao, M. Du, K. Zou, Q. F. He, C. Li, Unusual 3D ZnII coordination networks with
mixed tetrahedral and square-planar building units: from 2-fold interpenetrating bbf architecture to
self-penetrating 86 topological frameworks. CrystEngComm. 13 (2011), pp. 3355–3359.
[33] Liu. W, Ye. L, Liu. X, Yuan. L, Jiang. J, Yan. C, Hydrothermal syntheses, structures and luminescent
properties of d10 metal–organic frameworks based on rigid 3,3′,5,5′-azobenzenetetracarboxylic acid.
CrystEngComm. 10 (2008), pp. 1395–1403.
[34] R. E. Osta, M. Frigoli, J. Marrot, N. Guillou, H. Chevreau, R. I. Walton, F. Millange, A lithium–organic
framework with coordinatively unsaturated metal sites that reversibly binds water. Chem. Commun. 48
(2012), pp. 10639–10641.

ACCEPTED MANUSCRIPT
[35] D. Saha, T. Maity, S. Koner, A magnesium-based multifunctional metal-organic framework: synthesis,
thermally induced structural variation, selective gas adsorption, photoluminescence and heterogeneous
catalytic study.Dalton trans. 42 (2013), pp. 13912–13922.
[36] M. Mazaj, T. Birsa Čelič, G. Mali, M. Rangus, V. Kaučič, N. Zabukovec Logar, Control of the Crystallization
Process and Structure Dimensionality of Mg–Benzene–1,3,5-Tricarboxylates by Tuning Solvent
Composition. Cryst. Growth Des. 13 (2013), pp. 3825–3834.
[37] D. Banerjee, J. Finkelstein, A. Smirnov, P.M. Forster, L.A. Borkowski, S. J. Teat, J. B. Parise, Synthesis and
Structural Characterization of Magnesium Based Coordination Networks in Different Solvents. Cryst.
Growth Des. 11 (2011), pp. 2572–2579.
[38] D. Banerjee, J. B. Parise, Cryst. Recent Advances in s-Block Metal Carboxylate Networks. Growth Des. 11
(2011), pp. 4704–4720.
[39] Spek, A. L. PLATON, A Multipurpose Crystallographic Tool; Utrecht University: Utrecht, The Netherlands,
2002.
[40] H. Y. Ren, R. X. Yao, X. M. Zhang, Enhanced Catalysis Activity in a Coordinatively Unsaturated
Cobalt-MOF Generated via Single-Crystal-to-Single-Crystal Dehydration. Inorg. Chem. 54 (2015), pp.
6312–6318.
[41] L. M. Fan,W. L. Fan, B. Li, X. Zhao, X. T. Zhang, Structural diversities and related properties of four
coordination polymers synthesized from original ligand of 3,3′,5,5′-azobenzenetetracarboxylic acid. Dalton
Trans. 44 (2015), pp. 2380–2389.
[42] P. Y. Du,W. Gu, X. Liu, Three types of lanthanide coordination polymers from 1D to 3D based on a
tetracarboxylate ligand: synthesis, structural diversities and properties. CrystEngComm. 18 (2016), pp.
5140–5148.
[43] J. Zhao, D.-S. Li, X. -J. Ke, B. Liu, K. Zou, H.-M. Hu, Auxiliary ligand-directed structural variation from 2D
→3D polythreaded net to 3-fold interpenetrating 3D pillar-layered framework: Syntheses, crystal structures
and magnetic properties. Dalton Trans. 41 (2012), pp. 2560–2563.
[44] W. Liu, L.Ye, X. Liu, L. Yuan, J. Jiang, C. Yan, Hydrothermal syntheses, structures and luminescent
properties of d10 metal–organic frameworks based on rigid 3,3′,5,5′-azobenzenetetracarboxylic acid.
CrystEngComm. 10 (2008), pp. 1395–1403.
[45] D.-S. Li, X.-J. Ke, J. Zhao, M. Du, K. Zou, Q.-F. He, C. Li, Unusual 3D ZnII coordination networks with

ACCEPTED MANUSCRIPT
mixed tetrahedral and square-planar building units: from 2-fold interpenetrating bbf architecture to
self-penetrating 86 topological frameworks. CrystEngComm. 13 (2011), pp. 3355–3359.
[46] M. Meng, D.-C. Zhong, T.-B. Lu, Three porous metal–organic frameworks based on an
azobenzenetricarboxylate ligand: synthesis, structures, and magnetic properties. CrystEngComm. 13 (2011),
pp. 6794–6800.
[47] F. Xing, J. Jia, L. Liu, L. Zhong, M. Shao, Y.-l. Bai, Y. Zhao, S. Zhu, X. He, M. Li, Synthesis, structure and
adsorption of coordination polymers constructed from 3,3′,5,5′ -azobenzenetetracarboxylic acid and Zn ions.
CrystEngComm . 15 (2013), pp. 4970–4980.
[48] S. Zhang, J. Ma, X. Zhang, E. Duan, P. Cheng, Assembly of Metal–Organic Frameworks Based on
3,3′,5,5′-Azobenzene-tetracarboxylic Acid: Photoluminescences, Magnetic Properties, and Gas Separations.
Inorg. Chem. 54 (2015), pp. 586–595.
[49] M. Arıcı, O. Z.Yeşilel, M.Taş, H. Demiral, Effect of Solvent Molecule in Pore for Flexible Porous
Coordination Polymer upon Gas Adsorption and Iodine Encapsulation. Inorg. Chem. 54 (2015), pp. 11283–
11291.

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Table 1.
Compound
1
Empirical formula
C26MgN6O12H32
644.87
Formula weight
Temperature/K
298
Crystal system
Monoclinic
C2/c
space group
a/Å
10.7621(3)
21.2484(6)
15.5667(5)
90
b/Å
c/Å
α/°
β/°
102.881(3)
90
γ/°
Volume /Å3
Z
3470.17(18)
4
ρcalc (g/cm3)
ꢀ/mm-1
1.161
0.106
F (000)
1264.0
θ for data collection
3.09 to 25.00°
Reflections collected/unique 2461 / 3053
R (int)
0.0199
197
Parameters
GOF on F2
1.091
R1, wR2 [I > 2δ (I)]
R1, wR2 (all data)
0.0563, 0.1802
0.0563, 0.1880
Largest diff. peak/hole /e·Å-3 0.47/ -0.33

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Table 2.
Mg (1) -O (5a)
2.0645(19)
2.0824(16)
2.1057(15)
89.47(12)
90.79(7)
88.11(7)
Mg (1) -O (5)
2.0645(19)
2.0824(16)
2.1057(14)
172.22(6)
172.22(6)
88.11(7)
Mg (1) -O (1)
Mg (1) -O (1a)
Mg (1) -O (4b)
Mg (1) -O (4c)
O (5) -Mg (1) -O (5a)
O (5a) -Mg (1) -O (1a)
O (5a) -Mg (1) -O (4b)
O (5) -Mg (1) -O (4b)
O (5) -Mg (1) -O (1)
O (1a) -Mg (1) -O (4c)
O (1a) -Mg (1) -O (4b)
O (1a) -Mg (1) -O (1)
O (5) -Mg (1) -O (1a)
O (5a) -Mg (1) -O (1)
O (5) -Mg (1) -O (4c)
O (5a) -Mg (1) -O (4c)
O (1) -Mg (1) -O (4c)
O (1) -Mg (1) -O (4b)
O (4b) -Mg (1) -O (4c)
94.35(7)
90.79(7)
84.12(6)
93.43(6)
89.99(9)
94.35(7)
93.43(6)
84.12(6)
176.54(10)
Symmetry codes: a) - x, + y, 1/2 - z; b) -1/2 - x, 1/2 - y, -z; c) 1/2+x, 1/2-y, 1/2+z; d) -x, 1-y, -z
Table 3. The stability of reported compound.
Publish
Time
MOF Formula
Ligand
Stability
Temperature
315℃
Ref.
[ (H3O)2Mg(abtc) · (DMI)2]
[Co(H2abtc)(4,4-bipy)0.5(H2O)]
[Co3(H2abtc)3(btb)(H2O)6
[Cd(abtc)0.5(phen)]4·4H2O
[Zn3(abtc)(py)4(OH)2]
H4abtc
H4abtc
H4abtc
H4abtc
H4abtc
H4abtc
H3abtc
2012
2012
2008
2008
2011
2011
2013
2013
2015
2015
2015
2015
300℃
29
29
33
33
32
31
30
30
30
40
40
40
300℃
380℃
220℃
[Zn(abtc)0.5(bip)]·H2O
340℃
[Cd(HABTC)(H2O)2]·3H2O
350℃
[Zn2(η6-ao2btc)(η2-2,2'-bpy)2(H2O)2]·2H2O H4ao2btc 230℃
[Zn2(η8-aobtc)(η2-phen)(H2O)]·DMF
[Cd2(abtc)(DMA)2]·2(DMA)
[Zn2(ꢀ6-ao2btc)(ꢀ-obix)2]
H4aobtc 300℃
H4abtc
390℃
H4ao2btc 279℃
H4ao2btc 239℃
H4ao2btc 347℃
[Zn2(ꢀ4-ao2btc)(ꢀ-obix)2]
[Zn2(ꢀ4-ao2btc)(ꢀ-mbix)2]

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Table 4. Cyanosilylation of benzaldehyde in the presence of different Mg-MOF loadings
entry Cat. mol %
TMSCN
2 eq
Temp.(℃)
Time (h)
Conv.%
>99
1
2
3
1
r.t.
r.t.
r.t.
2
2
2
0.5
0.1
2 eq
>99
2 eq
>99
Determined by GC based on the carbonyl substrate.

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Table 5.
Time
(h)
Entry
substrate
product
Conv.%
>99
12
6
1
2
94
O
H
12
97
3
12
2
40
4
5
>99
12
12
>99
>99
6
7
12
12
97
8
9
>99

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Research highlight



A highly stable porous Mg-abtc MOF has been synthesized by solvethermal method.
Compound 1, with azo-group acting as Lewis base, has highly catalysis activity.
The catalyst can be reused up to five time without obvious loss of activity.