Ultrasound-assisted synthesis of two new fluorinated metal-organic frameworks (F-MOFs) with the high surface area to improve the catalytic activity

Article abstract of DOI:10.1016/j.jssc.2018.10.046

Micro- and nano-structures of two zinc(II) based fluorinated metal-organic frameworks (F-MOFs) [Zn₂(hfipbb)₂(4-bpdh)].(DMF)_0.5 (TMU-55) and [Zn₂(hfipbb)₂(4-bpdb)].(DMF)₂ (HTMU-55) with micr

Full text of DOI:10.1016/j.jssc.2018.10.046

Author’s Accepted Manuscript
Ultrasound-assisted synthesis of two new
Fluorinated Metal−Organic Frameworks (F-MOFs)
with the high surface area to improve the catalytic
activity
Monika Joharian, Ali Morsali
www.elsevier.com/locate/yjssc
PII:
S0022-4596(18)30485-7
https://doi.org/10.1016/j.jssc.2018.10.046
YJSSC20455
DOI:
Reference:
To appear in:
Journal of Solid State Chemistry
Received date: 30 September 2018
Revised date: 25 October 2018
Accepted date: 31 October 2018
Cite this article as: Monika Joharian and Ali Morsali, Ultrasound-assisted
synthesis of two new Fluorinated Metal−Organic Frameworks (F-MOFs) with
the high surface area to improve the catalytic activity, Journal of Solid State
Chemistry, https://doi.org/10.1016/j.jssc.2018.10.046
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Ultrasound-assisted synthesis of two new Fluorinated Metal−Organic
Frameworks (F-MOFs) with the high surface area to improve the catalytic
activity
Monika Joharian and Ali Morsali*
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115-
4838, Tehran, Islamic Republic of Iran
* Tel: +98-21-82884416, Email: morsali_a@modares.ac.ir
Abstract
Micro- and nano-structures of two zinc(II) based Fluorinated metal-organic framework (F-MOFs)
[Zn2(hfipbb)2(4-bpdh)].(DMF)0.5 (TMU-55) and [Zn2(hfipbb)2(4-bpdb)].(DMF)2 (HTMU-55) with micro- and
nanorods and nanospheres morphology were prepared via sonochemical route under ultrasonic irradiation
without any surfactants at room temperature. These new micro and nano-structures were characterized by
different techniques. To examine the effect of synthesis method on the porosity of the frameworks N2 adsorption
(BET analysis) was applied. The influence of sonication time and various concentrations of initial reagent on the
morphology and size of the F-MOFs nanostructures were investigated. The results indicated that by increasing
the time of ultrasonic radiation and concentration, smaller nanostructures form and morphological changes
occurred. These two frameworks with the presence of hydrophobic fluoro groups near the basic reaction center
in the F-MOFs are interesting candidates as an efficient catalyst in the Henry reaction for a comparative
catalytic study. This investigation indicates the important role of the F-MOFs nanostructures synthesized by the
ultrasonic method with the high surface area as heterogeneous catalysts with remarkable catalytic activity
compared with other MOFs.
Graphical abstract:

Micro- and nano-structures of two zinc(II) based Fluorinated metal-organic framework (F-MOFs) (TMU-55)
and (HTMU-55) were prepared via sonochemical route under ultrasonic. These two frameworks with the
presence of hydrophobic fluoro groups near the basic reaction center in the F-MOFs are interesting candidates
as an efficient catalyst in the Henry reaction for a comparative catalytic study. This investigation indicates the
important role of the F-MOFs nanostructures synthesized by the ultrasonic method with the high surface area as
heterogeneous catalysts with remarkable catalytic activity compared with other MOFs.
Keywords
Heterogeneous catalyst; F-MOFs; ultrasonic irradiation; Henry reaction.
Introduction
During the last two decades, metal-organic frameworks (MOFs) which are designed by the
association of metal ion clusters and organic ligands, as an innovative group of porous
materials with great potentials in catalysis, drug delivery, photocatalysis, gas storage, and
sensing have received considerable interest [1-5]. Taking advantage of MOFs over
conventional porous materials, many chemists have tried to design and synthesize various
MOFs having particularly desired structures and properties for certain applications.
Even though the using of metal-organic frameworks (MOFs) as the heterogeneous catalyst is
the earliest designed applications that proposed for these porous materials, compared with the
reported crystalline MOFs, the number of catalytically active structures is really limited [6,7].
Unlike common porous materials (e.g. zeolites, activated carbons, and mesoporous silicas),
MOFs have good thermal stability and large surface area so they can be used in the catalysis
reactions, such as Friedel-Crafts, Henry reaction, Hydrogenation of olefins, Knoevenagel
condensation reaction, etc. [8-16].
The Henry, also known as the nitro-aldol reaction, is one of the most useful carbon-carbon
bond forming reactions in modern organic chemistry and is used to synthesize b-nitro

alcohols from a nitroalkane and an aldehyde or a ketone [17]. The reaction itself has been
discovered in 1895 [18] and can be catalyzed by organic and inorganic bases [19-21].
Recently, some MOFs and discrete complexes were reported by Karmakar research group to
catalyze this reaction efficiently [22,23]. Nevertheless, it is still challenging to develop new
types of heterogeneous catalysts based on MOFs, displaying a high activity under mild
conditions and able to recycle.
A number of different synthetic approaches Such as solvothermal conditions [24], microwave
[25], sonochemical [6,26-28], and mechanochemical techniques [29] have been developed for
the preparation of metal-organic frameworks. Consequently, various kinds of chemical
reactions can proceed using ultrasonic irradiation [30,31]. Reducing the size of MOFs and
coordination polymers to nano-scale using ultrasound irradiation mostly via an increase of
crystallization nuclei has been widely reported [32-34]. In recent years, powerful ultrasound
radiation for many kinds of nanomaterial synthesis as a green energy source has been used
since ultrasound presents a simple, fast, cost-effective and environmentally friendly approach
for the preparation of nano-sized particles and compounds with new morphologies and
unique properties [35-37]. A comparison of the size of nanomaterials with bulk materials
indicated that the ratio of surface area to volume is also increasing the potential applications
of nanomaterials such as the catalytic activity.
Recently researchers have paid attention to the possibility of synthesizing fluorinated metal–
organic frameworks (F-MOFs) as a new class of advanced porous material. Compared to
metal–organic frameworks, F-MOFs with fluorinated channels or cavities are expected to
have increased catalytic activity, thermal stability, higher gas affinity, and selectivity, etc.
[38, 39].
As a part of our ongoing efforts in the design and synthesis of facile and environmentally
friendly nano-scale materials with high surface area to improve catalytic activity, we wish to
report herein on the synthesis of nanostructures of the F-MOFs, {[Zn2(hfipbb)2(4-
bpdh)]·(DMF)0.5 (TMU-55) and [Zn2(hfipbb)2(4-bpdb)].(DMF)2 (HTMU-55), (4-bpdb = 1,4-
bis(4-pyridyl)-2,3-diaza-1,3-butadiene,
4-bpdh
=
2,5-bis(4-pyridyl)-3,4-diaza-2,4-
hexadiene), and H2hfipbb = 4,4'-(hexafluoroisopropylidene) bis(benzoic acid)), which were
synthesized by the reaction of Zinc(II) acetate dihydrate, 4-bpdh, 4-bpdb, and H2hfipbb
ligands under ultrasonic irradiation without any surfactants at ambient temperature and
atmospheric pressure. Control of particle size and morphology and finally surface area were
enhanced in this synthesis method. Two F-MOFs were synthesized in three different

concentrations of initial reagents (0.005, 0.01 and 0.05 M) and two different reaction times of
15, and 60 min. Because of the unique properties of these nano-scale fluorinated metal–
organic frameworks (NFMOFs) and the high surface area in comparison of bulk materials,
they have been used in catalytic reactions. These nanostructure frameworks exhibited good
catalytic activity and they can show more catalytic efficiency because of the higher surface
area than bulk samples.
2. Experimental
2.1. Materials and measurements
All reagents for the synthesis and analysis were commercially available from Aldrich and
Merck Companies and used as received. Ligand 2,5-bis (4-pyridyl)-3,4-diaza-2,4- hexadiene
(4-bpdh) and 4-bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene was prepared by reported
method [40]. Melting point was measured on an Electrothermal 9100 apparatus. IR spectra
were recorded on a Thermo Scientific Nicolet IR100 (Madison, WI) Fourier-transform
infrared (FT-IR) spectrometric the range 500–4000 cm-1 using the KBr disk technique. Gas
chromatography (GC) runs were performed on an Echrom GC A90 gas chromatograph.
Ultrasonic generation was carried out in an ultrasonic bath SONICA-2200 EP with an
adjustable power output (frequency of 40 KHz). Powder X-ray diffraction (PXRD)
measurements were performed using a Philips diffractometer of X’pert company with
monochromated Co-kα (k = 1.78897Å) radiation. The molecular structure scheme and
simulated XRD powder patterns based on single crystal data were prepared using Mercury
(CSD) software. The samples were characterized by a scanning electron microscope (SEM)
TESCAN VEGA3 with gold coating.
2.2. Sonochemical synthesis of the TMU-55 and HTMU-55 nanostructures under
ultrasonic irradiation
Ultrasonic synthesis of TMU-55 and HTMU-55 were carried out in an ultrasonic bath at
room temperature and atmospheric pressure, operating with a power output of 305 W. To
prepare the nano-sized TMU-55 and HTMU-55, a solution of zinc(II) acetate dihydrate with
the certain concentration in DMF (10ml) was placed in an ultrasonic bath. Into this solution, a
mixed-ligand solution of H2hfipbb and 4-bpdh or 4-bpdb in DMF dropwise were added and
sonicated for 60 min (Scheme 1). The resulting precipitates were isolated by centrifugation,
washed with DMF and then dried in air for characterization. For further studies, these series

of experiments were performed in three different concentrations of all reagents (0.005, 0.01
and 0.05 M), two different times (15 and 60 min) and the power (12 W) (Table 1).
Selected IR peaks (cm-1) for TMU-55 nanostrcture: 3031(w), 2915(w), 1673(s), 1637(vs),
1550(w), 1403(vs), 1249(s), 1180(w), 1172(m), 833(m).
Selected IR peaks (cm-1) for HTMU-55 nanostrcture: 3039(w), 2908(w), 1658(m), 1627(s),
1558(m), 1396(s), 1241(s), 1172(s), 941 (w).
(H2hfipbb)
(L1)
(L2)
Scheme 1. The synthetic route used for the synthesis of TMU-55 and HTMU-55 and chemical
structure of the ligands used for the construction of TMU-55 and HTMU-55.
3. Results and discussion
The solvothermal reaction of Zn(NO3)2.6H2O and H2hfipbb as carboxylate ligand with ‘‘4-
bpdh’’ or ‘‘4-bpdb’’ ligand and in 1:1:1 mol ratio at 80°C for 72 h yields yellow crystals of
[Zn2(hfipbb)2(4-bpdh)]·(DMF)0.5 (TMU-55), and [Zn2(hfipbb)2(4-bpdb)].(DMF)2 (HTMU-
55), which is suitable for X-ray crystallography [16, 41], while micro/nano-structures of them
were obtained in DMF by ultrasonic irradiation at room temperature only in several minutes.
In order to evaluate the role of ultrasound irradiation in syntheses of the F-MOFs nano-
structures with the high surface area and finally improvement of their applications, we used
the sonochemical method for the synthesis of these F-MOFs.
Scheme 1 gives an overview of the methods used for the synthesis of TMU-55 and HTMU-
55 using the two different routes.

Crystal structure of HTMU-55 has been confirmed by comparison of powder pattern with the
calculated from the known structure (HUQFEG) [42]. Single crystal X-ray analysis of TMU-
55 reveals that it is isoreticular with HTMU-55 and HUQFEG. Determination of the structure
of these compounds by X-ray crystallography showed that they crystallize in the monoclinic
C2/c space groups [16, 41]. The coordination geometry around Zn(II) can be described as
distorted square pyramidal with the five coordination sites occupied by four oxygen atoms of
carboxylate groups from hfipbb ligands and one pyridyl nitrogen atom from the 4-bpdh (4-
bpdb) ligand (Figure 1). The 3D framework is constructed from paddle-wheel Zn2(COO)4
clusters bridged by hfipbb bent ligands to form a 2D square grids (sql) further connected by
the pillar ligands (4-bpdh or 4-bpdb) (Figure 1).
The single 3D framework is the rare self-catenated 6T9 net with (44.610.8) point symbol. The
6T9 topology, according to ToposPro database [43], is observed only in 13 isoreticular
structures, including HUQFEG. Ten of them have the same formula and SBUs as TMU-55
with M metals like Zn, Cu, Co, Cd, bent ligands such as hfipbb and oba (4,4’-
oxybisbenzoate) [42-52]. Moreover, the unit cell parameters are very similar and all
crystallize in the same monoclinic C2/c space group, showing a strong propensity toward the
6T9 net. This converts the 2-fold 2D interpenetration in the resulting single 3D self-catenated
net called 6T9

Fig 1. Crystal structure of [Zn2(hfipbb)2(4-bpdh)].(DMF)0.5 (TMU-55): (a) Ortep view of the asymmetric unit.
(b) {Zn2} paddlewheel building unit. (c) View along the crystallographic b-axis showing the disposition of the
clathrate DMF molecules along the helical channels. (d) Topology of [Zn2(hfipbb)2(4-bpdh)].0.5DMF (TMU-
55). Left: view of the underlying self-interpenetrated 6T9 net where the simplified 2-fold interpenetrated sql
layers (black) are connected by 4-bpdh ligand (green).
The IR spectra of both the micro and nano-structures produced by the sonochemical method
and of the bulk materials produced by the solvothermal method were compared with each
other in Figure 2.
Fig. 2. IR spectra of TMU-55 (left) and HTMU-55 (right) synthesized with solvothermal method (a) and
synthesized with sonochemical method (b).
Figures 3 and 4 show the simulated XRD pattern from single crystal X-ray data of TMU-55
and HTMU-55 in comparison with the XRD pattern of TMU-55 and HTMU-55 prepared by
the sonochemical method. The desirable accommodation was observed between the
simulated and experimental XRD patterns. These demonstrate that the compounds which are
acquired by the sonochemical process as nanostructures are an adjustment to that obtained by
single crystal diffraction. These results indicate that the TMU-55 and HTMU-55 received by

the sonochemical method are structurally in the good agreement and similar to that received
by the solvothermal method.
Fig 3. PXRD patterns of simulated pattern based on single crystal data of TMU-55 (a), Micro and nano-
structures of TMU-55 prepared in an ultrasonic bath (b), after catalytic reaction of TMU-55 (c), and after
catalytic reaction of TMU-55 nanostructure (d).
Fig 4. PXRD patterns of simulated pattern based on single crystal data of HTMU-55 (a), Micro and nano-
strucures of HTMU-55 prepared in an ultrasonic bath (b), after catalytic reaction of HTMU-55 (c), and after
catalytic reaction of HTMU-55 nanostructure (d).
The morphology and size of TMU-55 and HTMU-55 prepared by the sonochemical method
were characterized by scanning electron microscopy (SEM) by changing two parameters:
sonication time, and concentration of starting materials. Figures 5 and 6 show the SEM of
the TMU-55 and HTMU-55 prepared by ultrasonic generator 12W in concentration of initial
reagents [Zn2+] = [4-bpdh or 4-bpdb] = [H2hfipbb] = 0.005 mol.L-1 at 15 and 60 min (Figures
5a, 5b, 6a and 6b, respectively). For TMU-55, the size of nanostructures decreases over the
sonication time. For HTMU-55, the morphology of nanostructures changes from nanosphere
to nanorod over the sonication time. In order to examine the role of the concentration of

initial reagents on the morphology and size, experiments were performed by changing the
concentration of reagents in the range of 0.005–0.05 mol.L−1 (Table 1). Comparison between
the samples with different concentrations (Figures 7-10) shows that high concentrations of
initial reagents decreased particle size for TMU-55 and HTMU-55 and changed morphology
from nanosphere to nanorod for HTMU-55.
Table 1. Comparison of the morphology and size of micro/nano-structured of TMU-55 and HTMU-55 in
different conditions.
compound
TMU-55
Concentration (M)
Time (min)
Morphology
0.005
15
60
Rod -like
Rod -like
0.01
0.05
15
60
Rod -like
Rod -like
15
60
Rod
Rod
Sphere
Rod
15
60
0.005
0.01
0.05
15
60
Rod
Rod
HTMU-55
15
60
Rod
Rod
Thus, particle size produced using lower concentrations and sonication time 15 min of initial
reagents (0.005 mol L-1, Figures 5, 6) are bigger than particle size produced using higher
concentrations (0.01 and 0.05 mol L-1, Figures 7 - 10). More interestingly that, as shown in
Figures 9,10, increasing of concentration of initial reagents ultimate to prepared particle
nanostructure of the TMU-55 and HTMU-55.

Fig 5. SEM image of TMU-55 micro-structures obtained from 0.005 M concentration of the initial precursor in
an ultrasonic bath. a) 15 min, and b) 60 min.
Fig 6. SEM image of HTMU-55 micro-structures obtained from 0.005 M concentration of the initial precursor
in an ultrasonic bath. a) 15 min, and b) 60 min.
Fig 7. SEM image of TMU-55 micro-structures obtained from 0.01 M concentration of the initial precursor in
an ultrasonic bath. a) 15 min, and b) 60 min.

Fig 8. SEM image of HTMU-55 micro-structures obtained from 0.01 M concentration of the initial precursor in
an ultrasonic bath. a) 15 min, and b) 60 min.
Fig 9. SEM image of TMU-55 nano-structures obtained from 0.05 M concentration of the initial precursor in an
ultrasonic bath. a) 15 min and b) 60 min.
Fig 10. SEM image of HTMU-55 nano-structures obtained from 0.05 M concentration of the initial precursor in
an ultrasonic bath. a) 15 min and b) 60 min.
To study nitrogen sorption at 77 K of the nanostructures and the single crystals of TMU-55
and HTMU-55, the behavior of microporous materials analyses (BET) were performed.
TMU-55 showed limited porosity and HTMU-55 showed to be non-porous material
(negligible N2 uptake). N2 isotherm at 77 K on TMU-55 and HTMU-55 nanostructures
(Figure 11) showed a characteristic type I behavior of nano porous materials, as expected
2
-1
from its crystal structure (BET area (ABET) = 400.3 and 403.3 m .g for TMU-55 and HTMU-

55, respectively). These results showed that the surface area for nanostructures synthesized
by the ultrasonic method is the higher value than bulk samples synthesized by the
solvothermal method. As a result, they can show more catalytic efficiency because of the
higher surface area.
Fig. 11. N2 isotherm at 77 K and 1 bar collected on TMU-55 and HTMU-55 nanostructure after activating at
120 °C overnight under vacuum.
Catalytic studies
To explore the ability of TMU-55 and HTMU-55 nanostructures with the smaller size and
high surface area as heterogeneous catalysts in the catalytic reaction in comparison of bulk
samples, Henry reaction was selected.
Their catalytic performance in the Henry reaction of benzaldehyde with nitromethane was
investigated as shown in Scheme 2. TMU-55 and HTMU-55 specially TMU-55 with methyl
groups displayed good catalytic activity (71% and 68%, respectively) because of increasing
basicity and better interaction between azine groups (as Lewis base) in catalyst and substrate
but when nanostructures of these frameworks were used as catalysts in the Henry reaction,
they showed the high conversion (97% and 87%, respectively) because of higher surface
area.

Scheme 2. A representation of the Henry reaction catalyzed by TMU-55 and HTMU-55 nanostructures.
The reaction with benzaldehyde in methanol and in the absence of catalyst gave 6%
conversion as obtained by GC (Table 2). Using a suitable solvent can significantly increase
the yield of the reaction. In the first step of the catalytic reaction examinations, in order to
optimize the reaction solvent, we selected a range of solvents (Figure 12) and found that
methanol is the best solvent which could assist the reaction to proceed with high yield (97%).
Table 2. Henry reaction performed in the presence of the two isoreticular F-MOFs catalysts (TMU-55, HTMU-
55, and nanostructures of them) and in their absence.
Entry
catalyst
TMU-55
Conversion (%)
1
71
97
68
87
6
TMU-55 nanostructure
HTMU-55
2
3
HTMU-55 nanostructure
-
GC yield, Reaction conditions: benzaldehyde (0.2 mmol), nitromethane (0.5 mmol), 15 mg (3 mol%) catalyst,
solvent: methanol (3ml), 60°C, 24 h.
Fig 12. The reaction of benzaldehyde with nitromethane in the presence of TMU-55 and HTMU-55
nanostructures in different solvents. Reaction conditions: benzaldehyde (0.2 mmol), nitromethane (0.5 mmol),
15 mg catalyst, solvent (3ml), 60°C, 24 h.
Also, we evaluated the amount of catalyst on the reaction yield. Figure 13 compares the
results for the reactions performed with 2, 7, and 15 mg catalyst. During the survey of the

reaction conditions, the best results were obtained by using 15 mg of the catalysts at 60°C in
3 ml of methanol.
Fig 13. The reaction of benzaldehyde with malononitrile in the presence of TMU-55 and HTMU-55
nanostructures in different amount of catalysts. Reaction conditions: benzaldehyde (0.2 mmol), malononitrile
(0.5 mmol), solvent (H2O): (3ml), r.t, 5 min.
Then the reaction was proceeded using other aldehydes as substrates to compare the catalytic
activity of the F-MOFs nanostructures in the presence of electron-donating or withdrawing
groups. The results showed that the catalytic activity was enhanced by increased N-donor
ligands basicity (Table 3).
Table 3. Henry reaction catalyzed by the two isoreticular F-MOFs nanostructures catalysts (TMU-55, and
HTMU-55 nanostructure) in the presence of different aromatic aldehydes.
Entry
Catalyst
(nanostructure)
TMU-55
Substrate
Substrate
Product
Conversion (%)
97
87
1
HTMU-55
TMU-55
HTMU-55
68
60
2
3
4
TMU-55
HTMU-55
61
52
TMU-55
HTMU-55
100
92

TMU-55
HTMU-55
99
90
5
F-MOFs and F-MOFs nanostructures can be recycled and are reusable at least for 3 runs
without significant loss of their efficiency indicating the stability of the frameworks during
the catalytic reaction (Figures 14, 15). PXRD patterns and SEM images after catalytic
reaction are shown in Figures 3, 4, and 16, indicating the maintenance of both bulk and
nanostructure frameworks after the catalytic reaction. Also, the SEM images of bulk TMU-55
and HTMU-55 showed plate-like morphology with the size about 5 micrometer.
Fig 14. The PXRD patterns of (a) simulated from single crystal X-ray data of TMU-55 nanostructure,
(b) TMU-55 nanostructure as the catalyst after the third reaction run in Henry reaction.
Fig 15. The PXRD patterns of (a) simulated from single crystal X-ray data of HTMU-55 nanostructure,
(b) HTMU-55 nanostructure as the catalyst after the third reaction run in Henry reaction.

Fig 16. SEM images of as-synthesized TMU-55 (a), TMU-55 nanostructure (b), as-synthesized HTMU-55 (c),
and HTMU-55 nanostructure (d) before and after catalysis reaction.

In addition, Leaching test of these catalysts was carried out for the zinc ions by ICP analysis.
It was found that less than 1% of the zinc atoms from the frameworks pass into the reaction
solution, thus confirming, more than 99% of the zinc metal center does not leach into the
reaction mixture during the reaction conditions. These analyses prove the stability of the base
catalysts during the reaction.
Our study reveals that, when nanostructure samples as catalyst were used, the higher
conversions than the bulk structures were obtained because of the increased surface area.
Although there are some reports on MOFs [53, 54] which are catalytically active for this kind
of reaction at the higher temperature or more time reaction with other substrates, the yields
and conversions are usually higher for our compounds as compared to other metal–organic
frameworks (Table 5).
A comparison of the catalytic activity of TMU-55 and HTMU-55 nanostructures with some
MOFs that have been used as catalysts in the Henry reaction is shown in Table 5. To
demonstrate the advantages of our catalyst over other heterogeneous catalysts used in the
Henry reaction between benzaldehyde and nitromethane, we compared the obtained results
based on the amount of catalyst, the solvent used, different aldehydes, and the reaction time
(Table 5). The results obtained in this work were considerably higher in comparison with the
most given values in the literature for this reaction. HTMU-55 nanostructure shows a better
or comparable conversion with those of other reported MOFs.
Table 5. A comparison of the catalytic activity of various catalysts in the Henry reaction of benzaldehyde and
nitromethane.
Entry
Catalyst
Amount
Time
Solvent
Temp.
Conversion
Ref.
[°C]
(%)
1
2
3
4
[{Cu(L1)(DMF)}.DMF.H2O]n
[{Cu(L1)(DMF)}.DMF.H2O]n
[Zn(Lc)(H2O)2]n
2mol%
5mol%
10 mol%
40 h
84 h
36 h
72 h
MeOH
H2O
75
39
55
55
23
23
75
70
70
17
59
85
MeOH
[Zn3(TCPB)2∙2H2O]∙ 2H2O∙4DMF
Solvent free
10mol%
5
6
7
8
9
[Cu4(HLala)2(H2O)4(MeO)4]n
TMU-55 bulk
3mol%
3mol%
3mol%
3mol%
3 mol %
24h
24 h
24 h
24 h
24 h
MeOH
MeOH
MeOH
MeOH
MeOH
70
60
60
60
60
87
71
97
68
87
22
This work
This work
This work
This work
TMU-55 nanostructure
HTMU-55 bulk
HTMU-55 nanostructure
Conclusion

Two new three dimensional isoreticular F-MOFs nanostructures [Zn2(hfipbb)2(4-bpdh)].
(DMF)0.5 (TMU-55) and [Zn2(hfipbb)2(4-bpdb)]. (DMF)2 (HTMU-55) with different pillars
were synthesized by sonochemical method and characterized by different techniques. These
F-MOFs that have limited porosity were used as new solid base catalysts in the Henry
reaction given the basic character of the N-donor pillar ligands. These F-MOFs
nanostructures exhibit good catalytic activity with excellent conversions well in methanol
media because of the increased surface area. These results reveal that a sonochemical method
is an effective approach for the quick and simple preparation of nanostructures and very
promising method for synthesis of nano-scale MOFs. The better catalytic activity of TMU-55
is attributed to the presence of the methyl groups on the N basic centers in 4-bpdh that
enhance the basicity of the nitrogen active centers. This study demonstrates the important role
of the basicity of azine functionalized frameworks, as well as that of the high surface area of
the frameworks on the catalytic performance.
Acknowledgment
Support of this investigation by Tarbiat Modares University is gratefully acknowledged.
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Highlights:

 Synthesis of two new zinc(II) based Fluorinated metal-organic framework (F-MOFs)
by ultrasonic irradiation.
 Investigation of effects of sonication time and concentration on the morphology and
size.
 Investigate the important role of the F-MOFs nanostructures synthesized by the
ultrasonic method with the high surface area as heterogeneous catalysts with
remarkable catalytic activity compared with other MOFs.