Solvent-assisted ligand exchange (SALE) for the enhancement of epoxide ring-opening reaction catalysis based on three amide-functionalized metal-organic frameworks

Article abstract of DOI:10.1039/c9dt00941h

In recent years, functionalized pillar ligands have gained significant interests due to their important role in MOF structure and performance. The synthesis of MOF compounds with a particular functionalized ligand is not always successful, and sometimes, synthesis cannot be achieved easily or directly, even by employing several methods. However, this limitation can be overcome by applying a post-synthesis step that swaps the functional groups without changing the backbone of the pillar ligand. Solvent-assisted ligand exchange (SALE) is a post-synthesis method that has been used for confronting this challenge by replacing a functional group with an alternative. Through this investigation, we tried to improve the properties of MOF compounds and increase their catalytic efficiency by importing new functional groups into their structures. The N1,N3-di (pyridine-4-yl) malonamide linker (S) is a pillar ligand, which does not easily enter into the structure during the synthesis of MOF compounds. Therefore, to solve this issue, amide-functionalized, benzene-core ligand derivatives were designed as linkers to manufacture the new 3D structures [Co(oba)(bpta)]·(DMF)₂ TMU-50 and [Co₂(oba)₂(bpfn)]·(DMF)_2.5 TMU-51 and the novel 2D structure [Co(oba)(bpfb)]·(DMF)₂ TMU-49. These structures were achieved by layering the compounds via hydrothermal reaction. Moreover, the ability of these structures to act as catalysts was evaluated using the methanolysis reaction of epoxides. To increase the MOF catalytic efficiency, we designed the N1,N3-di (pyridine-4-yl) malonamide linker (S) as a malonamide pillar ligand, which contains an acidic hydrogen that is suitable for catalyzing an epoxide ring-opening reaction and therefore enhancing the catalytic activity. As the synthesis of the MOF structure with this linker was not successful, we designed three new structures by incorporating different percentages of S linkers by exchanging the acylamide functional group with malonamide via the SALE pathway. The acylamide functional group was successfully replaced and produced daughter MOFs TMU-49S, TMU-50S and TMU-51S. PXRD and NMR spectroscopy confirmed that the S linker was incorporated into the acylamide-MOF structure. The obtained materials TMU-49S, TMU-50S and TMU-51S are isostructural with their parent frameworks. The S spacer significantly improved the catalytic properties of the MOF compounds in the ring-opening reaction of epoxides, with TMU-50S showing a 98% catalytic efficiency after incorporating the S linker. The catalysts could be recycled without any significant loss in the catalytic efficiency.

Full text of DOI:10.1039/c9dt00941h

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Solvent-Assisted Ligand Exchange (SALE) For Enhancement of the
Capability of Epoxide Ring-Opening Reaction Catalysis Based on Three
Amide-Functionalized Metal-Organic Frameworks
a
a
a*
b
‡
‡
Maniya Gharib , Leili Esrafili , Ali Morsali , Pascal Retailleau
aDepartment of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115-175,
Tehran, Iran. E-mail: Morsali_a@modares.ac.ir;
bService de Cristallochimie, Institut de Chimie des Substances Naturelles-CNRS, Bât 27, 1 Avenue de la
Terrasse, 91190 Gif sur Yvette, France
‡M.Gh. and L.E. contributed equally to this work.

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Abstract
Over the past years, functionalized pillar ligands have been considered significantly due to their
important role in MOFs structure performance. Synthesis of MOFs compound with particular
functionalized ligand is not always successful, and sometimes it cannot be synthesized easily and
directly even by means of several methods. Hence, this limitation can be overcome by applying a post
synthesis way which is swapping functional groups without changing the whole backbone of pillar
ligand. Solvent-assisted ligand exchange (SALE) is a post synthesis method which has been assisted to
confront this challenge by replacing functional groups together. Through this investigation, we tried to
improve the properties of the MOFs compound and increase their catalytic efficiency by importing a
new functional group into their structures. N1, N3-di (pyridine-4-yl) malonamide linker (S) is one the
pillar ligands which does not easily enter to the structure in order to synthesize MOFs compound.
Therefore, to solve this issue , amide functionalized benzene-cored ligand derivatives were designed as
linkers for manufacture of new 3D structures of [Co(oba)(bpta)]•(DMF)2 TMU-50,
[Co2(oba)2(bpfn)]•(DMF)2.5 TMU-51 and one novel 2D [Co(oba)(bpfb)]•(DMF)2 TMU-49 , layered
of compound via hydrothermal reaction. Moreover, their ability as catalysts were figured out in the
methanolysis reaction of the epoxides. To increase the MOFs catalytic efficiency, we designed N1,
N3-di (pyridine-4-yl) malonamide linkers (S) as a malonamide pillar ligand, which consists of an
acidic hydrogen which is suitable for catalysis an epoxide ring-opening reaction that enhance the
catalytic activity. Due to the synthesis the MOFs structure via this linker was not possible, we tried to
design three new structures with incorporating different percentages of S linkers and exchange
acylamide functional group was with malonamide via SALE pathway. The acylamide functional group
was successfully replaced and produced daughter MOFs TMU-49S, TMU-50S and TMU-51S. PXRD
and NMR spectroscopy confirmed that the S linker is incorporated to acylamide-MOFs structure. The
obtained materials TMU-49S, TMU-50S and TMU-51S, are isostructural to their parent frameworks.
The S spacer significantly improved the catalytic properties of MOFs compound in ring-opening
reaction of epoxides and TMU-50S showed 98% catalytic efficiency after incorporated S linker. They
can be recycled without any significant loss of the catalytic efficiency.
Keywords: Metal Organic Frameworks; Ring opening of epoxide; Heterogeneous Catalysis.

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Introduction
A new class of crystalline inorganic-organic hybrid materials, Metal-Organic Frameworks (MOFs) 1-4
,
enable a chance for merging the inorganic building blocks and organic linkers to construct great
catalytic materials. Their crystalline structure valuable active sites, high surface area, permanent
porosity and chemical and thermal stability are the key features of this materials for catalytic activity.
Unlike common porous adsorbents (e.g. zeolites, mesoporous silicas and activated carbons), the pore
size and surface area properties of MOFs can be modulated by changing the sizes of the linkers 5-8 and
using pillar ligands with different functional groups 9-10 .However MOF-based catalysis was suggested
approximately 20 years ago and experimentally displayed 15 years ago11,lately wide experimental
investigation was done. As a result, heterogeneous catalysis was one of the earliest designed
applications for crystalline metal-organic framework (MOF) materials 12-16. The cases that affect the
catalytic activity of the metal-organic frameworks include, the Lewis acidity of the metal cations 17-20
,
the presence of basic groups 21-26 (such as pyridine, amide and amine) in forming linkers and the redox
properties of the metal centers27-29. Based on catalytic active sites, metal-organic frameworks are
sorted into four categories in terms of catalyst type, as follows: metal-organic frameworks with open
metal sites (I)30-32, MOFs with metalloligands (II), MOFs with functional organic sites (III) and metal
nanoparticles accommodated in the MOF cavities (IV).The functional group of organic ligands plays
an important role as linkers of MOFs backbone in catalytic activity which they can show host-guest
interaction with substrate. But sometimes, direct synthesis of MOFs structure by a particular
functionalized pillar is not possible so we faced a new challenge in synthesis method. Solvent-assisted
ligand exchange (SALE) is a post-synthesis way which has been helped us to confront this challenge
by replacing functional groups together. In this study, by introducing a malonamide functional group
into the structure, we tried to improve the features of the MOFs compound and increase their catalytic
performance and efficiency. N1, N3-di(pyridine-4-yl) malonamide linker (S) is one the pillar ligand
which cannot directly enter to the structure for synthesis MOFs compound. As for this approach, first
we reported synthesis of three novel catalytic compounds containing acylamide functional group
which is appropriate for catalyzing the ring opening reaction of epoxides due to its acidic properties.
Alcoholysis is a reaction in which the epoxides ring is opened via alcoholic compounds. This reaction
was selected as a pattern to investigate the catalytic activity of the synthesized parent compound
containing amide linkers and daughter samples including S spacers. The product of alcoholysis

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reaction of epoxides is 1,2-bifunctional compounds such as 1,2-diols, β-amino alcohols and other
useful compounds for the pharmaceutical and agrochemical 33-34. In order to activation the oxygen
atom of the epoxides it requires Lewis or Brønsted acid as a catalyst. In the traditional way, for a
35
36
catalytic heterogeneous system of polymers and materials based on silica , they used sulfuric acid
to achieve the methanolysis of epoxide. In recent years, remarkable studies have been conducted on
the use of MOFs which have metal Lewis acidity center as catalyst 37-38in methanolysis reaction.
Because of the coordination propensity of the solvent such as methanol which acts as a nucleophile on
the one side, and the necessary open metal sites within the MOF catalyst on the other side creates a
weak structural stability of these kinds of catalysts39. As a result, incorporating the linkers containing
Brønsted acids40-41or hydrogen-bond donating (HBD) sections in a MOF compound can provide a
stable MOF catalytic system during reaction process. The chosen pillar ligands are N,Nʹ-(1,4-
phenylene)diisonicotinamide (bpfb), N,Nʹ-bis(4-pyridinyl)-terephthalamide (bpta), and N,Nʹ-bis-(4-
pyridylformamide)-1,5-naphthalenediamine (bpfn), Fig. 1, that lead to synthesis of:
[Co(oba)(bpfb)]·(DMF)2 TMU-49; where DMF is (N,Ndimethylformamide); [Co(oba)(bpta)]·(DMF)2
TMU-50, which is the acylamide group in this compound is reversed in comparison to TMU-49; and
[Co2(oba)2(bpfn)]·(DMF)2.5 TMU-51, in which the use of the naphthyl analogue also effect on pore
size and enforce the acylamide groups are more orientated into the cavities towards TMU-50 and
TMU-49. To enhance the MOFs catalytic efficiency, we proposed to design N1, N3-di(pyridine-4-yl)
malonamide linkers (S), which have powerful acidic hydrogen in its functional group and suitable for
catalytic reaction that needs an acidic catalyst. Through the synthesis, MOFs structure with this ligand
under various conditions was not possible, so the S linker introduced to MOFs structure via SALE
method. SALE has appeared as a considerable strategy for exchange functional group and synthesis of
metal−organic frameworks (MOFs) which are unobtainable via traditional synthetic ways. For this
target, N1, N3-di (pyridine-4-yl) malonamide (S) linkers are replaced with acylmide pillars by the
SALE pathway. The pillar ligands were successfully replaced in these MOFs to produce daughter
MOFs TMU-49S, TMU-50S, and TMU-51S. The resultant materials are isostructural to the parent
framework and in each case contain malonamide moieties. The activity and efficiency yield of
catalytic reactions were enhanced especially in TMU-50S toward TMU-50 compound and exhibited 98
% yield efficiency for 32 hours. The malonamide functional group in the S spacer are favorable for
catalysis due to its ability to organize enol and ketone form and provide the highly acidic hydrogen
which is required for the epoxide ring-opening reaction.

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Fig. 1: N1, N3-di(pyridine-4-yl) malonamide(S), N,Nʹ-bis(4-pyridinyl)-terephthalamide (bpta), N,Nʹ-(1,4-
phenylene)diisonicotinamide (bpfb) and N,Nʹ-bis-(4-pyridylformamide)-1,5-naphthalenediamine (bpfn) linkers
Experimental
Materials and Characterization
All reagents for the syntheses and analysis were commercially available and used as received. The
infrared spectra were recorded on a Nicolet Fourier Transform IR, Nicolet 100 spectrometer in the
range 500-4000 cm-1 using the KBr disk technique. Thermo gravimetric analysis (TGA) of the title
compounds was performed on a computer-controlled PL-STA 1500 apparatus were carried out in a
Perkin Elmer Pyris 1 under N2 atmosphere and heating rate of 10 °C/min. X-ray powder diffraction
(XRD) measurements were performed using a Philips diffractometer of X’pert company with
monochromated Cu-kα (λ= 1.54056 Å) radiation. Elemental analyses were collected on a CHNS
1
Thermo Scientific Flash 2000 elemental analyzer. H NMR spectra were recorded on a Bruker 500
MHz NMR spectrometer.

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Synthesis of parent MOFs:
Synthesis of TMU-49, 50, 51
0.298 g of Co(NO3)2.6H2O (1 mmol), 0.258 g of oba (1 mmol) and 0.318 g of synthesized bpfb ligand
(1 mmol) were dissolved in 15 ml of N,N΄-Dimethylformamide (DMF) to synthesized the TMU-49.
The mixture was then placed in Teflon-lined stainless steel autoclaves and heated to 120 °C for 2 days.
The mixture was then cooled to room temperature over 24 hours. The same procedure was applied
with 0.318 g of bpta (1 mmol), and 0.368 g(1 mmol) of bpfn for synthesis of TMU-50 and TMU-51
respectively. Pale pink crystals were obtained as pure phases with a 36% synthesis yield for TMU-49,
45% synthesis yield for TMU-50 and purple crystals were acquired as pure phases with a 38%
synthesis yield for TMU-51. Then washed by DMF to removed residual impurity molecules, and dried
at room temperature.
Data for TMU-49. FT-IR (cm−1): 1673 (vs), 1597 (vs), 1540 (m), 1510 (m), 1399 (vs), 1309 (m),
1220(vs), 1159 (s), 1088 (m), 1067 (m), 1014 (m), 801 (m), 658 (m), 524 (m). EA on solvent free
sample: calcd. (%) for C35 H29 Co N5 O8: C, 59.5; H, 4.14 Co, 8.34; N, 9.91; O, 18.25; found: C, 59.96;
H, 4.2 Co, 8.12; N, 8.98; O, 18.41.
Data for TMU-50. FT-IR (cm−1): 1691 (m), 1595 (vs), 1504 (s), 1395 (vs), 1331 (m), 1298 (m), 1238
(vs), 1160 (vs), 1098 (m), 777 (m), 659 (m), 524 (m). EA on solvent free sample: calcd. (%) for C32
H24 Co N4 O7: C, 60.46; H, 3.81 Co, 9.27; N, 8.82; O, 17.62; found: C, 60; H, 3.7 Co, 9.6; N, 8.78; O,
17.69.
Data for TMU-51.FT-IR (cm−1): 1667 (vs), 1595(vs), 1570 (m), 1505 (s), 1386 (vs), 1235(s), 1158
(vs), 1089(m), 1065 (m), 1015 (m), 878 (m), 659 (m), 522 (m). EA on solvent free sample: calcd. (%)
for C56H46Co2N6O14: C, 58.75; H, 4.05 Co, 10.30; N, 7.34; O, 19.56; found: C, 58.32; H, 4.21 Co,
10.04; N, 8.35; O, 19.08.
Synthesis of TMU-49S, 50S and 51S via SALE to exchange the functional group
1 mmol (0.8 g) of TMU-49, 50 and 1 mmol (1.2 g) of TMU-51 MOF was placed in 15 mL of a DMF
solution containing 2 mmol (0.512 g) of S ligand. The reaction mixture was located in an oven at 80
°C and the proceeding of SALE was monitored by 1H NMR. The ligand solution was replaced every
day. After 5 days, 1HNMR demonstrated that 83% of bpfb, 67% of bpta and 47% of bpfn was replaced
by S ligand, respectively.

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Results and Discussion
Crystal structure explanation
TMU-49, [Co(oba)(bpfb)]•(DMF)2 (H2oba: 4,4’-oxydibenzoic acid; bpfb= N,Nʹ-(1,4-
phenylene)diisonicotinamide), was synthesized by combining Co(NO3)2•6H2O, the H2oba ligand and
bpfb amide-based pillaring ligand using solvothermal method at 120°C for 48 h to give suitable X-ray
quality crystals. TMU-49 crystallizes in the triclinic system with Pī space group. The asymmetric unit
contains one oba ligand and one bpfb as N donor ligand. The coordination geometry around the Co(II)
can be described as disordered octahedral with the six coordination sites occupied by four oxygen
atoms of carboxylate groups from three different oba ligands with different coordination modes and
two pyridyl nitrogen atoms from bpfb ligand (Fig. 2a). The 2D sheets are connected through the linear
bpfb ligands. Compound TMU-49 exhibit one-dimensional channel along b axis as shown in Fig. 2b.
Pores size is 25.186 Å including van der Waals radius which is shown most large pore in comparison
to compounds TMU-50 and TMU-51. Compound TMU-49 is two-fold interpenetrated as shown in
Fig. 2c. The internal surface of these pores is functionalized with the amide groups of the bpfb ligands,
which are shows in Fig.2d.
The new TMU-50, [Co(oba)(bpta)]•(DMF)2 , (H2oba: 4,4’-oxydibenzoic acid; bpta = N,Nʹ-bis(4-
pyridinyl)-terephthalamide), was produced via Solvothermal reaction between Co(NO3)2.6H2O, H2oba
and the bpta pillar ligand in DMF at 120 oC for 2 days and generated suitable X-ray quality crystals of
TMU-50. The simulated (derived from the single crystal structures) and experimental. X-ray
crystallography shows that TMU-50 crystallizes in the monoclinic crystal system and P21/n space
group. The structure of TMU-50 manufactured by a binuclear Co unit (Co1 and Co2). The
coordination geometry around the paddle-wheel structure of Co1-Co2 can be described as octahedral
with the six coordination sites occupied by four oxygen atoms of carboxylate groups from four
different oba ligands with different coordination modes and one pyridyl nitrogen atoms from bpta
ligand. Co1 is octahedrally coordinated to four carboxylate O atoms (O1, O3, O5, O7) from four oba
ligands, one N atom (N1) from the bpta ligand and Co2. Also, Co2 is coordinated in form of
octahedral to four carboxylate O atoms (O2, O4, O6 and O8) from four oba ligands, one N atom (N2)
from the bpta ligand and Co1. (Fig. 3a) The distance between Co1 and Co2 is 2.637 Å. Each binuclear

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Co2 unit is further linked to four equivalent neighbors through four oba ligands to give 2D sheets. The
2D sheets are connected through the linear bpta, extending the structure in three dimensions (Fig. 3b).
Compound TMU-50 is two-fold interpenetrated as shown in Fig. 3c.And shows one-dimensional 12.84
Å pores including the vander Waals radius. The internal surface of these pores is functionalized with
the amide groups of the bpta ligands, which are shown in Figure 3d.
The novel structure of TMU-51 crystallizes in the orthorhombic Pna21 space group. Thus, it also
consists of a 2-fold interpenetrated network that exhibits 1D pore channels of ≈ 14.83 Å functionalized
with acylamide groups. The orientations of acylamide groups are not toward the pores. The structure
of TMU-51 constructed from a binuclear Co2 unit (Co1 and Co2). The coordination geometry around
the Co1-Co2 can be described as distorted octahedral with the six coordination sites employed by four
oxygen atoms of carboxylate groups from three different oba ligands and one pyridyl nitrogen atoms
from bpfn ligand (Fig. 4a). Co1 is coordinated to four carboxylate O atoms (O1, O4, O7 and O10)
from four oba ligands, one N atom (N1) from the bpfn ligand and Co2. Also, Co2 is coordinated in
form of octahedral to to four carboxylate O atoms (O2, O5, O6 and O9) from four oba ligands, one N
atom (N4) from the bpta ligand and Co1. The distance between Co1 and Co2 is 2.719 Å. Each
binuclear Co2 unit is further linked to four equivalent neighbors through four oba ligands to give 2D
sheets. The 2D sheets are connected through the linear bpfn, extending the structure in three
dimensions (Fig. 4b). Compound TMU-51 is two-fold interpenetrated as shown in Fig. 4c. In Fig. 4d
shows the position of bpfn ligands between two Co-oba Secondary Building Units (SBU). Powder X-
ray diffraction (PXRD) patterns were shown in Fig. S1, corroborating that all synthesized MOFs can
be obtained as pure phases. The topological of structure TMU-50 showed that structure consists of 3D
framework with V2Ti5ScO2N2C2. The Point symbol for net is uninodal and 6-connected with point
symbol {4^4.6^10.8}. For TMU-49 topology the nets are sql/Shubnikov tetragonal plane net in
valence-bonded MOFs, standard and cluster representations, respectively. The topological showed the
net is uninodal and 4-connected with point symbol {4^4.6^2}. Also, the topology of the TMU-51 net is
mab in valence-bonded MOFs, cluster representation. Structure consists of 3D framework with
CrVTi2Sc4O2N2C2.There are 2 interpenetrating nets. From the topological point of view, the net is
uninodal and 6-connected with point symbol {4^4.6^10.8}.

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Fig. 2: Coordination environment around Co(II) in TMU-49 (a), View of the simplified two dimensional
structure (b), two-fold interpenetration of TMU-49 structure (c), internal surface of these pores is functionalized
with the amide groups of the bpfb ligands(d).

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Fig. 3: Coordination environment around Co(II) in TMU-50 (a), View of the simplified three dimensional
structure (b), two-fold interpenetration of TMU-50 structure (c) and internal surface of these pores is
functionalized with the amide groups of the bpta ligands (d).

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Fig. 4: Coordination environment around Co(II) in TMU-51(a), View of the simplified three dimensional
structure (b), two-fold interpenetration of TMU-51 structure (c), internal surface of these pores is functionalized
with the amide groups of the bpfn ligands(d).
The BET measurement for TMU-49 and TMU-51 exhibited that these compounds are nonporous
toward N2.(Fig. S3) The FT-IR spectroscopy, elemental analysis, and powder X-ray diffraction
(PXRD) confirmed the removal of guest DMF molecules accommodated in the pores of the
framework. The BET measurement showed that TMU-50 structure is porous toward N2 at 77 K;
Brunauer−Emmett−Teller (BET) surface area of 753 m2/g, (Fig. 5).

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Fig. 5: Nitrogen adsorption-desorption isotherms at 77 K. (a) TMU-50 and TMU-50S
Thermogravimetric analysis (TGA) of TMU-49, TMU-50 and TMU-51 shows a first weight loss in
200 °C (calcd 20%, found 20.5%), 180 °C (calcd 15%, found 15.2%) and 200 °C (calcd 20%, found
20.3%) respectively, which are attributed to the removal of DMF molecules inside the framework.
Then a second weight loss was observed at 350 °C for TMU-50 and 400 °C for TMU-49 and TMU-51,
corresponding to the decomposition of the framework. The final residual weight for TMU-49, 50 and
51 corresponds to that of cobalt oxide (Fig. S2).
To investigate the effect of SALE reaction on the BET surface area, cavity size and porosity of
daughter compounds, N2 adsorption/desorption was performed at 77 K and 1 bar on samples. The
results displayed that compound TMU-50S, with a Brunauer−Emmett−Teller (BET) specific surface
1
area of 509 m2/g and both TMU-49S and TMU-51S were non-porous compounds.(Fig.S3) H NMR
showed replacement of the parent bpta, bpfb and bpfn pillars by S linkers is 67%, 83%, and 47 %,
respectively (Fig. S4) after 5 days. The powder X-ray diffraction (PXRD) patterns of TMU-49, TMU-
50, and TMU-51 in comparison with their daughters (TMU-49S, 50S and 51S) confirmed that the
MOFs synthesized via SALE are structurally similar to their parents (Fig. 6).

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In addition, the color of parent crystals totally changed from pink into light brown which is represented
the light brown S linkers exchanged with acylamide pillars in daughter samples. (Fig. 7)
For the IR spectrum of TMU-50, 249 and 51, the amide NH stretch absorption can be observed at 3327
cm-1.The acylamide NH bending absorption is 1540 cm-1. The symmetric and asymmetric vibrations of
the carboxylate group are observed as two strong bands at 1640 and 1690 cm–1, respectively (Fig. S5).
Also as shown in Fig. S4 the IR spectrum of TMU-49S, 50S, and 51S with the characteristic peak for
1642 cm–1 for enol form of carbonyl are studied. Entrance the S ligand into the MOFs structure as
shown in NMR analysis has two resonance form (enol and keto form) which causes widespreadness
the IR peaks in 3000-3500 cm-1.
Fig. 6: PXRD of the as-synthesized TMU-49(black), TMU-50 (blue) and
TMU-51 (green), The PXRD of the as-synthesized TMU-49S (red), TMU-50S (pink) and
TMU-51S (dark blue).

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Fig.7: From left to right: color of parent crystals TMU-49, 50 and 51 changed from pink and purple into brown
in daughter samples TMU-49S, 50S and 51S after SALE via S.
Catalytic properties
Catalytic activity of new synthesized MOFs based on amide and malonamide pillar functional group,
are investigated in methanolysis reaction of epoxides. To explore the catalytic reaction condition, the
ring opening of the styrene oxide in MeOH was chosen. No methanolysis reaction at room temperature
occurred. In addition, no extra product was observed in the presence of mixed solvents including
toluene, CH2Cl2, CHCl3, THF and CH3CN in combination with MeOH (1:1 ratio) during 18 h reaction
with styrene oxide.
The alcoholysis reaction in the absence of catalyst, when the reaction temperature was increased to
60°C, during 24 and 32 h, the reaction proceeded with 13% and 16% conversions (Table 1, entries 1
and 2) while within 24 h, in the presence of 15 mg TMU-50S ,TMU-49S and TMU-51S, 86 ,23 and
16% of styrene oxide was converted as obtained by GC., respectively (entry 4).Whereas, this reaction
even among 32h in presence of 15mg parent MOFs(TMU-50, 49, 51) 43,25 and 18% of styrene

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oxide was converted, respectively which is shown low catalytic efficiency (Table 2,entiries 4). This
observation clearly revealed that the S linkers within daughter MOFs and BET surface area played an
important role in increasing catalytic efficiency. As specified, TMU-50S which is have high BET
surface area and S pillar ligands among other MOFs displayed remarkable catalytic activity.
Moreover, for optimization of the catalyst and also solvent amounts and the time, the same reaction
runs were performed. During the study of the reaction conditions in the presence of different amount
of catalysts in presence of the 15mg styrene oxide, the best results were obtained by using 15 mg of the
catalysts and at 60 ˚C in 3 ml of MeOH. Through the optimized reaction conditions for daughter MOFs
(TMU-50S, TMU-49S and TMU-51S), 100 (98% selectivity), 30, and 21 % of the corresponding
products were respectively formed after 32h (Table.1, entry 5).To investigate the stability of the
structure, heterogeneous feature of catalytic compounds and to prove that the functional group plays a
major role in the catalyst reaction, using a hot filtration test in addition to ICP analysis.
After 32 h of the methanolysis reaction of the styrene oxide, the reaction mixtures were centrifuged
and the catalysts were filtered off. Then, the remaining methanolic liquids were left stirred at 60 ̊C.
The interesting thing is that, within 32 h of further reaction time, no noticeable changes were
recognized in the reaction conversion via GC analysis. This was a proof of the non-interference of the
cobalt metal species as Lewis acid in epoxide activation during catalytic process.
Moreover, in order to confirm the stability of MOFs catalytic structure, the same reaction was
performed. The catalysts were filtered off after 32 h, washed thoroughly with MeOH and the filtrates
were examined by ICP analysis. 0.10, 0.14 and 0.19% of residual cobalt were identified for TMU-50S
,TMU-49S and TMU-51S, respectively which significantly confirmed more than 99% of the cobalt
metal center do not leach into reaction mixture during the methanolysis reaction.
All of these results, confirm reputable chemical stability of the synthesized MOFs structure and also
the powerful hydrogen bond donating feature of the malonamide moieties through the MOFs structure.
The productivity of all catalysts was evaluated by determination of the reaction selectivity for the
conversion of styrene oxide to 2-methoxy-2-phenylethanol as the major product in our catalytic
system. The main reason of increase catalytic efficiency of TMU-50S among TMU-49S and TMU-51S
is due to its porosity and BET surface area. According to BET results of these compounds, can be
concluded that compound TMU-50S between other compounds has the most porosity and BET surface
area therefore its catalytic performance is more than other compounds in mathanolysis styrene oxide
reaction. Due to the regioselectivity of the catalytic reaction and examined the effect of a substituent

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group on epoxides it was interesting for us to consider other epoxide derivatives in the mathanolysis
reaction. The reaction of four epoxides involving γ-phenoxypropylene oxide, allyl(2,3-
epoxypropyl)oxide, 2-(chloromethyl)oxirane and t-butyl styrene oxide was shown with all three
catalysts which are TMU-50S,49S and TMU-51S.(Table 1, entries 10-17). Although, the reactivity
changed in methanolysis of these substrates, 2-(chloromethyl)oxirane among the other epoxides
showed high catalytic activity in 24h due to its Cl substituent( electron withdrawing group) which is
accelerated the ring opening reaction (Table1, entry15).To reveal that the catalytic reaction occurs
within the cavity of MOFs framework, we investigated the methanolysis of t-butyl styrene oxide
substrate. According to Table 1 (entry 17) the methanolysis of t-butyl styrene oxide via TMU-50S and
TMU-51S proceeded insignificant even after 100 h but for TMU-49S it has been slightly different and
the catalytic efficiency was 30%. The higher efficiency among the other two catalysts is related to the
two dimensional and layered structure of TMU-49S.
For more investigate the comparison of the catalytic efficiency of these heterogeneous catalytic
systems, the time-conversion for these catalysts were plotted and compared with the control
methanolysis reaction of styrene oxide, Fig.8.Which is a presentation that compound TMU-50S due to
its porosity and high surface area in comparison other catalysts have more activity. In addition, to
appraise the catalyst recycling ability, TMU-49S, 50S, and 51S catalysts were filtered off after 40 h
reaction, washed with excess MeOH and dried at 80 ̊C and under vacuum at room temperature,
respectively. Also, the comparison of the PXRD patterns of recycle catalysts clearly show that XRD
patterns are similar to as-synthesized patterns and there is not any decrease in crystallinity occurred in
these recovered catalyst structures (Fig. S6). To increase the accuracy of the research, we used GC
mass analysis to identify the products and the substrate materials. Fig. S7 show the Chromatogram of
Control reaction and the reaction which is performed by catalysts. The mass spectroscopy of substrate
and product of the mathanolysis reaction led to more accurate product identification. Furthermore, this
data show the real heterogeneous character and actual chemical stability in the reaction.
Comparison of the maximum catalytic performance of MOF TMU-50S with those of the other catalyst
presented in the literature for epoxide ring opening reaction is listed in Table 3. As can be seen, the
characteristics of the proposed MOF catalyst are better than, or at least comparable to, those of other
sorbents reported for the ring-opening reaction of epoxides. The active acid sites of the examined
MOFs are either Lewis or Brønsted acids and most of them can achieve full conversion within a
reasonable time. Although it is difficult to make a comparison as different reaction conditions were

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used, the TMU-50S seems to be the best catalyst and has a relatively fast reaction rate. These
investigations explain the ability of this MOF to organize enol and ketone form of its malonamide
pillar ligand and provide the highly acidic hydrogen which is required for the epoxide ring-opening
reaction.

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Table 1. Methanolysis of epoxides by S-containing MOFs
a GC yield using internal-standard method; Conditions: styrene oxide (25 mg, 0.2 mmol), 60
̊C, methanol (3
mL). b with recycled catalysts. c The data in parenthesis are the selectivity calculated for the major product.

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Table 2. Methanolysis of epoxides by acylamide-containing MOFs
a GC yield using internal-standard method; Conditions: styrene oxide (25 mg, 0.2 mmol), 60
̊C, methanol (3
mL). c The data in parenthesis are the selectivity calculated for the major product.
Table 3. Comparison of the catalytic performance of TMU-50S with other reported MOF catalysts used for the
ring opening of styrene oxide
Compound name
Ligand Functional group
Catalytic
Time
Ref
efficiency
in ring opening
reaction of
epoxides
1,3,5-
Benzenetricarboxylate
(BTC)
4,4'-bipyridine (bpy)
&
[Fe(BTC)]
70
99
24h
3h
42
43
Cu(bpy)(H2O)2(BF4)2(bpy)
BF4−
Anion
MIL-101
BDC
44
48h
44
N1, N3-di (pyridine-4-yl)
malonamide &bpta
In this
work
TMU-50S
98
32
(urea-based ligand) is 4,4'-
(carbonylbis(azanediyl))dibenzoic
acid &bpy
[Zn2(ubl)2(bipy)]·DMF
100
140h
45

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Zr-Uio-66
HF-Uio-66
BDC
Biphenyl-4.4’-dicarboxylic acid
40
41
24h
24h
46
46
Fig. 8: Comparison of time conversion plot for methanolysis of styrene oxide catalyzed by
TMU-49S, TMU-50S, TMU-51S, and the reaction control system. Conditions: styrene oxide (0.2mmol),
catalyst (15 mg), 60 ̊C, methanol (3 mL); reaction control (without catalyst)
Theoretical calculations
To better investigate the interface between substrate interactions with different ligands in MOFs, we
first analyze the MEP plots of the isolated ligands. Fig. 9 displays the MEP isosurfaces on the 0.001 au

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electron density isosurface of these molecules, where positive and negative regions are expressive of a
nucleophilic and electrophilic site, respectively.
It is obvious from Fig. 9, that the negative MEP regions are majorly associated with the nitrogen or
oxygen atoms that demonstrate the potential of these sites to an electrophilic attack. More
interestingly, the most negative MEP in TMU-49, TMU-50, and TMU-51 is mainly associated with the
oxygen atom of acylamide group, further the negative MEP of the S ligand which is in all three TMU
compounds is mainly related to the oxygen atom of malonamide group. All these ligands are also
characterized by a distinguished negative area, associated with the nitrogen atom of pyridine. This
computational process fully confirmed the interaction between the substrate and the ligands.
Fig. 9: Electrostatic potentials mapped on the electron isodensity surface of ligand bpfb(a),bpta(b),bpfn(c) and
S(d)
Conclusion

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Three new 3D Co (II)-based MOFs (TMU-49, TMU-50, and TMU-51) incorporating a highly π-
conjugated amide functionalized organic ligand has been successfully synthesized under solvothermal
conditions. Moreover, their ability as catalysts was figured out in the regioselective methanolysis of
epoxides. To enhance the MOFs catalytic efficiency use Solvent-assisted ligand exchange reaction
(SALE) strategy, and replace N1, N3-di (pyridine-4-yl) malonamide linker (S), which have acidic
hydrogen suitable for catalysis an epoxide ring-opening reaction with amide-ligand and enhance
catalytic activity. For this aim, N1, N3-di (pyridine-4-yl) malonamide (S) linkers are exchanged with
amide pillars via SALE pathway and produce daughter MOFs TMU-49S, TMU-50S, and TMU-51S.
The obtained materials (MOFs TMU-49S, TMU-50S, and TMU-51S, respectively) are isostructural to
the parent frameworks. We observed that functional group had a significant effect on catalytic
properties of MOFs and increased the Metal-organic frameworks catalytic activity in the epoxide ring-
opening reactions. They can be recycled without any significant loss of the catalytic efficiency.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ??? Publications website at DOI:???
Experimental details, PXRD patterns, TGA, IR spectroscopy and sensing graphs and details (PDF)
Crystallographic data (CIF)
ACKNOWLEDGMENT
This work was funded by Tarbiat Modares University.
Refrences

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