Lanthanide metal organic frameworks based on dicarboxyl-functionalized arylhydrazone of barbituric acid: Syntheses, structures, luminescence and catalytic cyanosilylation of aldehydes

Article abstract of DOI:10.1039/c7dt01056g

Five isostructural lanthanide MOFs, [Ln(1κOO′,2κO′′,3κO′′′,4κO′′′′-μ₄-L)(NO₃)(DMF)₂]_n·n(DMF) {Ln = La³⁺ (1), Ce³⁺ (2), Nd³⁺ (3), Sm³⁺ (4) and Dy³⁺ (5); L =

Full text of DOI:10.1039/c7dt01056g

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L. Pombeiro, Dalton Trans., 2017, DOI: 10.1039/C7DT01056G.
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Lanthanide Metal Organic Frameworks based on dicarboxyl-
functionalized arylhydrazone of barbituric acid: Syntheses,
Structures, Luminescence and Catalytic Aldehydes Cyanosilylation
a
a
a
a
Anirban Karmakar *, Guilherme M. D. M. Rúbio , Anup Paul , M. Fátima C. Guedes da Silva ,
a,d
b,c
e
Kamran T. Mahmudov , Firudin I. Guseinov , Sónia A.C. Carabineiro and Armando J. L.
a
Pombeiro *
a
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais,
1
049–001, Lisbon, Portugal. E-mail: anirbanchem@gmail.com; pombeiro@tecnico.ulisboa.pt.
b
Department of Chemistry, M. V. Lomonosov Moscow State University, 1 Leninskie Gory, 119992
Moscow, Russian Federation.
c
National University of Science and Technology «MISIS», Moscow Leninsky prosp. 4, 119049
Moscow, Russian Federation.
d
Department of Ecology and Soil Sciences, Baku State University, Z. Xalilov Str. 23, Az 1148 Baku,
Azerbaijan.
e
Laboratório de Catálise e Materiais, Laboratório Associado LSRE-LCM, Faculdade de Engenharia,
Universidade do Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto, Portugal.
Abstract
Five isostructural lanthanide MOFs, [Ln(1κOO’,2κO’’,3κO’’’,4κO’’’’-
ꢀ
4
-L)(NO
La (1), Ce (2), Nd (3), Sm (4), Dy (5); L = 5-[2-{2,4,6-trioxotetrahydropyrimidin-5(2H)-
ylidene}hydrazinyl]isophthalate; DMF N,N’-dimethyl formamide}, based on dicarboxyl-
3 2 n
)(DMF) ] ·n(DMF) {Ln=
3
+
3+
3+
3+
3+
=
functionalized arylhydrazone of barbituric acid were synthesized under solvothermal conditions.
They were characterized by elemental analysis, FT-IR spectroscopy, thermogravimetric and X-ray
diffraction analyses. Crystal structure analysis revealed that these frameworks possess a similar type
-
of two dimensional (2D) structures with a dinuclear {Ln
2
(COO )
2
} unit acting as a secondary building
block. Topological analysis shows that these frameworks display a 3,6-connected kgd; Shubnikov
plane (3.6.3.6)/ dual net. They exhibit excellent heterogeneous catalytic activities (compound 2 is the
most active one) towards the cyanosilylation of aldehydes under solvent-free conditions. These
catalysts can be recycled at least up to five cycles without losing activity. Compounds 1-5 exhibit
luminescent properties in the solid state at room temperature.
Introduction
The design and construction of novel metal organic frameworks (MOFs) have been the object of a
1
substantial interest over recent decades as a new frontier for material research. This is due not only
to their attractive architectures and structural topologies but also to their potential applications in
2
heterogenous catalysis, sensing, magnetism, nonlinear optics and luminescence, etc. Lanthanide
based MOFs are particularly promising on account of the high and variable coordination numbers,
3
,4
flexible coordination geometries and oxophilic nature of lanthanide ions.
1

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The selection of ligands is also crucial to construct a high-dimensional Ln-MOF and it is noteworthy
5
the use of multidentate aromatic carboxylate ligands, due to their robustness and thermal stability.
On the other hand, barbituric acid containing carboxylate ligands are also excellent candidates for
the construction of unique structures and topologies because they have multiple coordination sites
6
and can adopt versatile conformations. Recently, we have reported the synthesis and application of
Zn(II) and Cd(II) coordination polymers based on dicarboxyl-functionalized arylhydrazone of
7
barbituric acid ligand. Now we wish to extend our work to lanthanide metal systems.
8
Microporous MOFs have attracted a wide attention for applications in heterogeneous catalysis,
9
10
11
such as Knoevenagel condensation, cyanosilylation of aldehydes or ketones, Henry reaction,
1
2-13
14
15
oxidation of alkane, alcohol or olefin,
Mukaiyama–aldol reaction, ring-opening of epoxides,
etc. Moreover, recently many Ln-MOFs have been applied as catalysts for various reactions, such as
1
6
17
18
oxidation of sulphur compounds, Henry reaction and cyanosilylation of aldehydes or ketones.
The MOFs containing an amide based ligand were found to be convenient for Lewis base catalysed
1
9
organic transformations. On the other hand, coordinatively unsaturated Ln(III) ions are capable to
1
6-18
function as active catalytic sites for Lewis acid promoting reactions.
Thus the combination of
unsaturated (or potentially so, with a labile ligand) lanthanide ions with an amide group containing
ligand should exhibit efficient Lewis acid and base-type catalytic performances at the same time.
Thus, in the present work, we have chosen the barbituric acid based pro-ligand 5-[2-{2,4,6-
trioxotetrahydropyrimidin-5(2H)-ylidene}hydrazinyl] isophthalic acid (H
five new isostructural Ln-MOFs formulated as [Ln(1κOO’,2κO’’,3κO’’’,4κO’’’’-
L)(NO )(DMF) ] ·n(DMF) {Ln= La (1), Ce (2), Nd (3), Sm (4), Dy (5); L = 5-[2-{2,4,6-
2
L) (Scheme 1) to construct
4
ꢀ -
3
+
3+
3+
3+
3+
3
2 n
trioxotetrahydropyrimidin-5(2H)-ylidene}hydrazinyl]isophthalate; DMF = N,N’-dimethyl formamide}.
These compounds have been characterized by elemental analysis, IR and photoluminescence
spectroscopy, thermogravimetric analysis and single-crystal and powder X-ray diffraction. We have
also performed the topological studies of these frameworks and have tested their heterogeneous
catalytic activity towards cyanosilylation of aldehydes and ketones under solvent free conditions.
Results and Discussion
Syntheses and Characterization
The five new isostructural Ln-MOFs were synthesized by using solvothermal reaction conditions. The
solvothermal reactions of 5-[2-{2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene}hydrazinyl]isophthalic
2
acid (H L) (Scheme 1) with different lanthanide salts in the presence of DMF and water at 75˚C leads
to the formation of the isostructural 2D frameworks [Ln(1κOO’,2κO’’,3κO’’’,4κO’’’’-ꢀ -
4
3
+
3+
3+
3+
3+
L)(NO
3 2 n
)(DMF) ] ·n(DMF) {Ln= La (1), Ce (2), Nd (3), Sm (4), Dy (5); L = 5-[2-{2,4,6-
trioxotetrahydropyrimidin-5(2H)-ylidene}hydrazinyl]isophthalate; DMF = N,N’-dimethyl formamide}.
2

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O
N
HN
NH
O
O
Ln(NO ) .6H O
3
3
2
[
Ln(L)(NO )(DMF) ] —n(DMF)
NH
3 2 n
o
DMF: H O, 75 C
2
48 h
Ln = La3+ (1), Ce3+ (2), Nd3+ (3),
Sm3+ (4), Dy3+ (5)
O
O
OH
OH
H2L
Scheme 1
The overall features of the FT-IR spectra for compounds 1-5 are similar in the region from 400 to
-
1
4
1
000 cm . The characteristic strong bands of the coordinated carboxylate groups appear at 1525–
-
1
-1
20
529 cm for the asymmetric stretching and 1384-1386 cm for the symmetric one. The C=O
-
1
stretching of amide groups appears between 1654 and 1661 cm and the NH of the amide groups
-1
are observed in the 3402-3422 cm range. Moreover they were also characterized by single crystal
X-ray diffraction, elemental and thermogravimetric analysis (supporting information, Figure S2).
Crystal Structure Analysis
According to the crystal structure analyses the solvothermal reactions between Ln(NO
3
)
3
.6H
L lead to the formation of the five new 2D frameworks 1-5
Figure 1), which are isostructural and crystallize in the triclinic P-1 space group. The structural
2
O (Ln =
3
+
3+
3+
3+
3+
La , Ce , Nd , Sm and Dy ) and H
2
(
motifs of these frameworks display a high resemblance with slight differences in the unit cell
parameters. As shown in Table S1 (supporting information), from La to Dy the unit cell parameters
decrease slightly.
Since the five structures (1-5) are isostructural, only that of 1 is described in detail herein as a
representative example. It is a neutral two dimensional (2D) metal–organic framework (Figure 1C)
3
+
which crystallizes in the triclinic space group P-1. The asymmetric unit of 1 contains one La ion, one
2
-
doubly deprotonated ligand (L ), one coordinated nitrate anion, two coordinated and one non-
coordinated dimethylformamide molecules (Figure 1A and 1D). As shown in Fig. 1B, the central La1
is nine-coordinated and shows distorted tricapped trigonal prism geometry. The coordination sphere
2
-
of La(III) ion is occupied with five oxygen atoms from four coordinated L ligands, two oxygen atoms
from the two coordinated DMF molecules, and two oxygen atoms from the chelating nitrate anion.
Ln'
O
O
O
N
O
N
O
O
O
O
O
HN
N
N
H
O
O
Ln
O
N
H
Ln''
Ln'''
O
O
O
O
N
3

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DOI: 10.1039/C7DT01056G
A
B
C
D
3
+
3+
3+
3+
3+
Figure 1: (A) The molecular structure of Ln-frameworks 1-5 (Ln = La , Ce , Nd , Sm and Dy ) with
partial labeling scheme. (B) Schematic representation of frameworks 1-5. (C) Two dimensional
packing diagram of Ln-frameworks 1-5. (D) Arrangements of DMF and nitrate molecules in
framework of 1-5 (arbitrary view).
The La–O (carboxylate) bond distances vary from 2.4042(18) to 2.5835(18)Å, and the La–O (amide)
bond distance is 2.6152(18) Å. Moreover the La–O (nitrate) and La–O (DMF) bond distances are
within 2.631(3)-2.649(3) Å and 2.495(2)-2.530(2) Å, respectively. The O–La–O bond angles vary from
4
7.60(9)° to 158.01(7)°. The metal-oxygen bond lengths are within the range of those usually
4
b-c
encountered for lanthanide-oxygen coordination. As expected the metal-oxygen bond distances
from compound 1 (La) to 5 (Dy) decrease slightly on account of the lanthanide contraction.
In framework 1, two crystallographically equivalent La(III) atoms are bridged by two carboxyl groups
2
-
-
from two different L ligands forming a dinuclear {La
2
(COO )
2
} building block unit. The dinuclear
2
-
clusters are interlinked via two L ligands forming 1D chains, which are further linked by the other
2
-
four L to construct a 2D framework with the metal-bound nitrate and DMF molecules directed
outwards on both sides. The bridging carboxylate group connects two La ions with the La⋯La
distance of 5.4554(3) Å, which does not indicate any significant direct interaction between the metal
atoms. The metal-metal distances from compound 1 to 5 decrease continuously.
o
Table 1: Selected bond angle ( ) and bond distance (Å) parameters of 1-5
1
2
3
4
5
4

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Ln1-Ocarboxylate
2.4042(18)-
.5835(18)
2.6152(18)
2.3767(18)-
2.5542(18)
2.595(2)
2.3470(19)-
2.528(2)
2.3188(19)-
2.4842(19)
2.531(2)
2.263(2)-2.432(2)
2.478(2)
2
Ln1-Oamide
Ln2-ONitrate
Ln2-ODMF
2.5589(19)
2.631(3)-2.649(3) 2.612(3)-2.624(3) 2.584(3)-2.588(3) 2.560(3)-2.562(3) 2.516(3)-2.526(3)
2.495(2)-2.530(2) 2.473(2)-2.612(3) 2.440(2)-2.481(2) 2.407(2)-2.459(2) 2.353(3)-2.422(2)
<
O-Ln-O
47.6(9)°-
48.04(9)°-
157.50(7)°
5.4279(3)
48.54(9)°-
156.60(7)°
5.4021(3)
49.05(9)°-
156.16(7)°
5.3705(3)
49.61(10)°-
155.23(8)°
5.3317(3)
1
58.01(7)°
Ln1-Ln1’
5.4554(3)
The non-coordinated DMF molecules are hydrogen bonded with amide NH- via N4-H4N···O13 (dD–A
.880(3) Å; <D–H····A 173.0˚) interactions. Another amide NH- group is also involved in hydrogen
2
bonding with a carboxylate oxygen via N3-H3N···O4 (dD–A 2.729(3) Å; <D–H····A 159.9˚) interaction.
Relevant hydrogen bond distances and angles are listed in Table S3 (supporting information).
Moreover, various C−H⋅⋅⋅O interactions are present in this structure which helps its expansion to the
third dimension.
21
To further study the structure of the frameworks 1-5, their topology was analyzed using TOPOS 4.0.
The crystal structures of 1-5 are very similar and their topological features are identical. To represent
the simplified net structure of these frameworks we consider the dinuclear {La (COO-) } building
2
4
2
-
block unit as a single node which is coordinated with 6 different carboxylate linkers (L ), whereas
each ligand is connected with three different metal centres and acts as a 3-connected node. Thus,
the structure can be simplified as a 3,6-connected kgd; Shubnikov plane (3.6.3.6)/ dual net with
3
6
6
3
2
point symbol (4 ) (4 ·6 ·8 ) (Figure 2).
Figure 2 Node-and-linker-type descriptions of the 2D coordination frameworks in 1-5. The metal
nodes are represented in green (Ln) and carboxylate linker in red color.
Catalytic activity
We have tested the activity of the five compounds 1–5 as heterogeneous catalysts in the aldehyde
cyanosilylation reaction under solvent-free conditions at room temperature (Scheme 2). Initially, we
3
have used benzaldehyde as a model substrate in the presence of different solvents (CH CN, THF,
CHCl and MeOH) and also without any added one. Solvent-free conditions result in the highest
3
catalytic activity, whereas the use of THF as solvent leads to the lowest one (entries 10 and 7, Table
5

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1
, Figure 4B). Thus, we have performed the cyanosilylation reaction by using a mixture of aldehyde,
trimethylsilyl cyanide (TMSCN) and a Ln-catalyst at room temperature under added solvent-free
conditions (TMSCN acted both as a reagent and a solvent).
Scheme 2
The reactions performed in the presence of frameworks 1-5 exhibited rapid conversions of
benzaldehyde into 2-phenyl-2-((trimethylsilyl)oxy)acetonitrile, reaching 89-94% yields after 2 h
reaction (entries 1-5, Table 1). Compound 2 shows the highest activity (entry 2) which, however, is
almost the same of that of 1 (entry 1). We have also checked the reactivity of lanthanide salts and
free ligand (H L) towards the cyanosilylation reaction and the obtained reaction yields are within 9-
2
1
8% (entries 17-22, Table 1). A blank test was carried out with benzaldehyde in the absence of any
catalyst at room temperature and yielded only 7% of the product after a reaction time of 2 h (entry
6, Table 1).
1
Table 1 Optimization of the parameters of the cyanosilylation reaction of benzaldehyde with trimethylsilyl
a
cyanide (TMSCN) with frameworks 1-5 as catalysts
b
c
Entry
Catalyst
Time (h)
Amount of
Solvent
Yield (%)
TON
Catalyst (mol%)
1
1
2
3
4
5
2
2
2
2
2
3.0
3.0
3.0
3.0
3.0
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
93
94
91
89
90
31
31
30
30
30
2
3
4
5
Different Solvents
6
7
8
9
1
2
2
2
2
2
2
2
2
2
2
3.0
3.0
3.0
3.0
3.0
CH
3
CN
47
43
55
61
94
16
14
18
20
31
THF
CHCl3
MeOH
0
Solvent free
Catalyst Amount
1
1
1
1
1
1
2
3
4
5
2
2
2
2
2
2
2
2
2
2
1.0
2.0
3.0
5.0
8.0
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
64
84
94
95
95
64
42
31
19
12
1
1
1
1
2
2
6
7
8
9
0
1
Blank
2
2
2
2
2
2
-
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
7
-
La(NO
Ce(NO
Nd(NO
Sm(NO
Dy(NO
)
.6H
.6H
.6H
.6H
.6H
O
3.0
3.0
3.0
3.0
3.0
14
16
18
11
13
5
5
6
4
4
3
3
2
)
O
2
3
3
3
)
3
2
O
3
)
3
2
O
3
)
3
2
O
6

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2
2
H2L
2
-
Solvent free
9
-
a
Reaction conditions: benzaldehyde (1 mmol), trimethylsilyl cyanide (500 µl, 4 mmol), 3.0 mol%
b
1
(
relative to the aldehyde) of catalyst, at room temperature. Calculated by H-NMR as the number of
c
moles of product 2-phenyl-2-((trimethylsilyl)oxy)acetonitrile per mole of aldehyde X 100. Number of
moles of product 2-phenyl-2-((trimethylsilyl)oxy)acetonitrile per mole of catalyst.
We have tested the effect of catalyst amount in the cyanosilylation reaction catalysed by 2. The
increase of the catalyst amount from 1.0 to 3.0 mol% enhances the product yield from 64 to 94%,
respectively (entries 11-13, Table 1), but a further increase of that amount (up to 8%) results only in
an insignificant yield improvement (entries 14 and 15, Table 1), with a marked decrease of the TON
value. Thus, we have performed the cyanosilylation reaction of benzaldehyde using 3 mol% (relative
to the aldehyde) of compound 2 as catalyst. The plot of yield vs. time (until 2 h) for the solvent-free
cyanosilylation reaction of benzaldehyde with TMSCN and 2 is presented in Fig. 4A. Upon further
extending the reaction time to 4 h, the product yield increased up to 99% but the TOF value
-
1
-1
decrease markedly (from 15.3 h to 8.2 h ). Moreover, no other products were detected and the
yield of this product corresponds to the conversion of benzaldehyde.
A
B
Figure 4 (A) Plot of 2-phenyl-2-((trimethylsilyl)oxy)acetonitrile yield vs. time for the cyanosilylation
reaction, catalysed by 2, of benzaldehyde with TMSCN at room temperature (dotted line concerns
the catalyst removal after 0.25 h: see text). (B) Yield of cyanosilylation of benzaldehyde in different
solvents catalysed by framework 2.
We have also explored the activity of catalyst 2 towards a variety of aromatic aldehydes and
ketones. The corresponding cyanohydrin derivatives were obtained with yields ranging from 31% to
9
8% (Table 2). Aryl aldehydes bearing strong electron-withdrawing substituents (nitro and chloro)
exhibit the highest yields (entries 1-3 and 4, Table 2) whereas the aldehydes containing electron-
donating groups (methyl or methoxy) show lower reaction yields (entries 8 and 9, Table 2). The
ortho-substituted substrates show lower reactivity than the meta- or para-subtituted ones,
conceivably due to steric hindrance. Moreover, the aromatic ketones show a much lower reactivity
1
4a, 18a
than the aromatic aldehydes, as obtained in other cases
.
Table 2: Cyanosilylation reaction between various aldehydes and ketones and trimethylsilyl cyanide with
a
catalyst 2
7

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b
c
Entry
Reactant
Yield (%)
TON
1
2
3
4
5
6
7
8
9
2-Nitrobenzaldehyde
3-Nitrobenzaldehyde
4-Nitrobenzaldehyde
4-Chlorobenzaldehyde
Salicylaldehyde
93
96
98
94
83
87
89
65
47
31
49
38
31
32
33
31
28
29
30
22
16
10
16
13
3-Hydroxybenzaldehyde
4-Hydroxybenzaldehyde
4-Methylbenzaldehyde
4-Methoxybenzaldehyde
Acetophenone
1
1
1
0
1
2
4-Chloroacetophenone
2-Hydroxyacetophenone
a
Reaction conditions: 3.0 mol% (relative to the aldehyde) of catalyst 2, trimethylsilyl cyanide (500 µl,
b
1
c
4
mmol) and aldehyde (1 mmol) for 2 h at room temperature; Calculated by H NMR; Number of
moles of product per mole of catalyst.
Table 3: A comparison of catalytic activity of various MOFs in the cyanosilylation reaction of benzaldehydes and
trimethylsilyl cyanide (TMSCN) under solvent free conditions
Solvent/Temp/Time
Aldehyde
Entry
Catalyst
Yield (%) Reference
1
2
3
4
5
6
2
Solvent free/RT/2h
Benzaldehyde
Benzaldehyde
Benzaldehyde
Benzaldehyde
Benzaldehyde
Benzaldehyde
94
78
84
99
98
90
This work
22a
o
[Pr(3,5-DSB)(Phen)]
Solvent free/50 C/3h
[Yb
OMe
2
(L)
2
(H
2
O)
3
].2H
2
O
Solvent free/RT/12h
Solvent free/RT/14h
Solvent free/RT/5h
Solvent free/RT/5h
22b
[Pr(L )(H O) ]·2.5DMA·3H O
22c
2
4
2
[Sm(H
2
O)
5
][Sm(H
2
O)
7
][Co
2
Mo10
H
4
O38]·6H
2
O
22d
[Ce(H O) ] Mo V O .8H O
2
5 2
6
2
26
2
22e
3
L
,5-DSB = 3,5-disulfobenzoic acid; Phen = 1,10-phenathroline; L = 4,4',4''-((2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene))tribenzoate;
OMe
= 3,3’-((2,3,6,7-tetramethoxyanthracene-9,10-diyl)bis(4,1-phenylene)) diacrylate.
A comparison of the activity of our catalyst 2 with other reported Ln-MOFs is shown in Table 3 for
the cyanosilylation of benzaldehyde with TMSCN. Our catalyst appears to be more effective. For
example, the cyanosilylation reaction of benzaldehyde and TMSCN catalysed by a Pr(III)-MOF of 3,5-
disulfobenzoic acid and 1,10-phenathroline leads to an overall yield of only 78% after 3h reaction
o
22a
time at 50 C under solvent free conditions (entry 2, Table 3). Moreover, the use of a 3D Yb(III)
2
2b
MOF results into an yield of 84% after 12h of reaction time (entry 3, Table 3). In the case of
another Pr(III)-MOF with 3,3’-((2,3,6,7-tetramethoxyanthracene-9,10-diyl)bis(4,1-phenylene))
2
2c
diacrylate, an yield of 99% is achieved after 14h (entry 4, Table 3), a much longer reaction time
than ours. An Evans–Showell type polyoxometalate framework of Sm(III) leads to an yield of 98%
2
2d
after 5h (entry 5, Table 3), also a longer time than in our case. Besides that, a lanthanide-
supported molybdovanadate MOF leads to an yield of 90% after 5h reaction time (entry 6, Table
2
).
2e
3
2
3
To check the heterogeneity of the catalyst 2 we have performed the following test for the
cyanosilylation reaction. We have removed the catalyst by centrifugation after 0.25 h (yield 55%)
and kept the catalyst-free reaction solution under the same conditions stirred for additional 1.75 h.
As shown in Fig. 4A (dotted line), after removal of the solid catalyst, the product yield did not
increase significantly. This demonstrates the heterogeneous nature of the catalyst. Moreover, we
8

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DOI: 10.1039/C7DT01056G
have also determined the amount of cerium in the reaction mixture after removing the catalyst 2
upon completion of the reaction. Only an insignificant amount (0.011% of the amount used in the
reaction) of cerium was present in the solution, thus ruling out any significant leaching of the
catalyst. We have also checked the structural integrity of the catalyst 2 after catalysis by performing
FT-IR and powder X-ray diffraction analyses of the catalyst before and after the catalysis reaction.
These results supports that the structure of the catalyst 2 remains intact after the catalytic reaction
(Figure S1).
We have also tested the recyclability of the catalyst 2. For this purpose, upon completion of a
reaction cycle, we have separated the catalyst by centrifugation, washed with dichloromethane and
dried at room temperature before further use. We have repeatedly recycled the catalyst 2 and the
catalytic system maintained almost the full activity for at least five consecutive cycles as shown in
Fig. 5.
Figure 5 Effect of the catalyst 2 recycling on the yield of 2-phenyl-2-((trimethylsilyl)oxy)acetonitrile.
OSiMe
3
H
R
CN
O
O Ln
R
H
H
R
H
CN
O
R
Me
3
Si
O
O Ln
O Ln
R
H
3
Me Si
CN
O
3
Me Si CN
O Ln
Scheme 3
9

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DOI: 10.1039/C7DT01056G
A possible catalytic cycle for the cyanosilylation reaction catalyzed by a Ln-MOF is proposed in
Scheme 3. It can involve dual activation of the carbonyl and TMSCN by the Ln(III) centre and a ligated
carboxylate group, respectively, followed by the formation of C-C bond leading to the
1
0f, 24
cyanohydrin.
Conclusion
In summary, we have synthesized five lanthanide (La, Ce, Nd, Sm and Dy) MOFs having similar
structures based on a novel dicarboxyl-functionalized arylhydrazone of barbituric acid ligand namely
5
-[2-{2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene}hydrazinyl]isophthalic
structurally characterized by single crystal X-ray diffraction analyses which reveal that they exhibit
D structures with interesting topologies.
acid.
They
were
2
Furthermore, these new materials containing lanthanides are efficient heterogeneous Lewis acid–
base catalysts for cyanosilylation of various aldehydes (ketones are much less reactive) under
solvent-free conditions at room temperature. The Ce(III)-MOF (framework 2) displays the highest
catalytic activity, followed by the La(III)-MOF (1) leading to high yields in short reaction times with a
low catalyst loading under solvent-free conditions at room temperature. In comparison with other
reported Ln-MOF based catalysts, our catalyst 2 is usually more efficient under identical conditions.
The stability and recyclability of the heterogeneous catalysts were demonstrated by various tests
and methods, the framework 2 remaining intact after the catalytic reaction. The results provide
further evidence that Ln-MOFs can be utilized as effective heterogeneous catalysts in essential
organic transformations, such as that of this work.
Experimental Section
The synthetic work was performed in air and at elevated temperature. All the chemicals were
-
1
obtained from commercial sources and used as received. The infrared spectra (4000–400 cm ) were
recorded on a Bruker Vertex 70 instrument in KBr pellets; abbreviations: s = strong, m = medium, w
=
weak, bs = broad and strong, mb = medium and broad. Carbon, hydrogen, and nitrogen elemental
analyses were carried out by the Microanalytical Service of the Instituto Superior Técnico. Thermal
properties were analyzed with a Perkin-Elmer Instrument system (STA6000) at a heating rate of 5˚C
-1
min under a dinitrogen atmosphere. Powder X-ray diffraction (PXRD) was conducted in a D8
Advance Bruker AXS (Bragg Brentano geometry) theta-2-theta diffractometer, with copper radiation
(Cu Kα, λ = 1.5406 Å) and a secondary monochromator, operated at 40 kV and 40 mA. Flat plate
configuration was used and the typical data collection range was between 5˚ and 40˚. Emission
spectra in solid state at room temperature were recorded on a Perkin Elmer Fluorescence
Spectrometer (LS-55). A sample was analysed by N
2
adsorption at −196ºC on a Quantachrome NOVA
4
200e apparatus. The specific surface area was calculated by the Brunauer–Emmett–Teller (BET)
2
5
equation.
1
0

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1
3 2 n
. Synthesis of [La(L)(NO )(DMF) ] ·n(DMF) (1)
3 3 2 2
A mixture of La(NO ) .6H O (26 mg, 0.06 mmol) and H L (10 mg, 0.03 mmol) was dissolved in 2 mL of
DMF and water (4 : 1). The resulting mixture was sealed in an 8 mL glass vessel and heated at 75˚C
-
1
for 48 h. Subsequent gradual cooling to room temperature (0.2 ˚C min ) afforded yellow crystals.
-
1
Yield: 83% (based on La). FT-IR (KBr, cm ): 3413 (bs), 1654 (s), 1528 (s), 1385 (s), 1273 (s), 1105 (m),
1
033 (w), 913 (w), 862 (m), 803 (m), 786 (w), 716 (m), 669 (w), 518 (m), 487 (m). Anal. Calcd. for
13 (M = 738.39): C, 34.16; H, 3.69; N, 15.18. Found: C, 34.43; H, 3.74; N, 15.13.
C
21 8
H27LaN O
2
3 2 n
. Synthesis of [Ce(L)(NO )(DMF) ] ·n(DMF) (2)
The procedure was the same as that for compound 1 except that La(NO ) ·6H O was replaced by
3
3
2
-
1
Ce(NO
273 (s), 1105 (m), 914 (w), 864 (m), 803 (m), 785 (w), 717 (m), 667 (w), 519 (m), 488 (m). Anal.
Calcd. for C21 13 (M = 739.62): C, 34.10; H, 3.68; N, 15.15. Found: C, 34.02; H, 3.62; N, 15.37.
BET surface area: < 5 m /g.
3 3 2
) ·6H O. Yield: 79% (based on Ce). FT-IR (KBr, cm ): 3422 (bs), 1660 (s), 1526 (s), 1385 (s),
1
8
H27CeN O
2
3
. Synthesis of [Nd(L)(NO
3 2 n
)(DMF) ] ·n(DMF) (3)
The procedure was the same as that for compound 1 except that La(NO ) ·6H O was replaced by
3
3
2
-
1
Nd(NO
270 (s), 1104 (m), 1035 (m), 916 (w), 862 (m), 805 (m), 785 (w), 717 (m), 667 (w), 519 (w), 488 (m).
Anal. Calcd. for C21 13 (M = 743.74): C, 33.91; H, 3.66; N, 15.07. Found: C, 33.73; H, 3.52; N,
3 3 2
) ·6H O. Yield: 76% (based on Nd). FT-IR (KBr, cm ): 3402 (bs), 1656 (s), 1529 (s), 1384 (s),
1
8
H27NdN O
1
5.32.
4
3 2 n
. Synthesis of [Sm(L)(NO )(DMF) ] ·n(DMF) (4)
The procedure was the same as that for compound 1 except that La(NO ) ·6H O was replaced by
3
3
2
-
1
Sm(NO
270 (s), 1105 (m), 1036 (w), 912 (w), 863 (m), 807 (m), 785 (w), 717 (m), 667 (m), 518 (m), 489 (m).
Anal. Calcd. for C21 13 (M = 749.85): C, 33.64; H, 3.63; N, 14.94. Found: C, 33.53; H, 3.55; N,
3 3 2
) ·6H O. Yield: 64% (based on Sm). FT-IR (KBr, cm ): 3415 (bs), 1661 (s), 1527 (s), 1386 (s),
1
H
8
27SmN O
1
4.75.
5
. Synthesis of [Dy(L)(NO )(DMF) ] ·n(DMF) (5)
3 2 n
The procedure was the same as that for compound 1 except that La(NO
3
)
3
·6H
O. Yield: 65% (based on Dy). FT-IR (KBr, cm ): 3411 (bs), 1661 (s), 1525 (s), 1385 (s),
270 (m), 1104 (m), 915 (w), 863 (m), 807 (m), 787 (w), 718 (m), 668 (w), 519 (m), 490 (m). Anal.
Calcd. for C21 13 (M = 762.00): C, 33.10; H, 3.57; N, 14.71. Found: C, 33.21; H, 3.41; N, 14.56.
2
O was replaced by
-
1
3 3 2
Dy(NO ) ·6H
1
H
8
27DyN O
Procedure for cyanosilylation reaction of aldehydes
A suspension of an aromatic aldehyde (1 mmol), trimethylsilyl cyanide (500 µl, 4 mmol) and 3 mol%
catalyst (22.1 mg for 1, 22.2 mg of 2, 22.3 mg of 3, 22.5 mg of 4 and 22.8 mg of 5; relative to the
aldehyde) was stirred at room temperature under solvent-free condition. After the desired time the
catalyst was removed by centrifugation and the reaction mixture was dissolved in CDCl
3
and
1
analyzed by H NMR (supporting information, Fig. S3).
1
1

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DOI: 10.1039/C7DT01056G
In order to perform the recycling experiment, the catalyst isolated by centrifugation was washed
with dichloromethane and dried at room temperature. The subsequent steps were performed as
described above.
Crystal structure determinations
X-ray quality single crystals of the compounds were immersed in cryo-oil, mounted in a nylon loop
and measured at room temperature (1-5). Intensity data were collected using a Bruker APEX-II
PHOTON 100 diffractometer with graphite monochromated Mo-Kα (λ 0.71069) radiation. Data were
collected using phi and omega scans of 0.5° per frame and a full sphere of data was obtained. Cell
2
6a
26a
parameters were retrieved using Bruker SMART software and refined using Bruker SAINT on all
2
6b
the observed reflections. Absorption corrections were applied using SADABS. Structures were
2
6c
26c
solved by direct methods by using the SHELXS-2014 package and refined with SHELXL-2014/6.
26d
Calculations were performed using the WinGX System-Version 2014.1. The hydrogen atoms
attached to carbon and nitrogen atoms were inserted at geometrically calculated positions and
included in the refinement using the riding-model approximation; Uiso(H) were defined as 1.2Ueq of
the parent atoms for phenyl and 1.5Ueq of the parent atoms for the methyl groups and nitrogen
atoms. Least square refinements with anisotropic thermal motion parameters for all the non-
hydrogen atoms and isotropic ones for the remaining atoms were employed. Crystallographic data
are summarized in Table S1 (Supplementary Information file) and selected bond distances and
angles are presented in Table S2. CCDC 1539686-1539690 contain the supplementary
crystallographic data for this paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgements
This work has been supported by the Foundation for Science and Technology (FCT), Portugal (project
UID/QUI/00100/2013). The work was also carried out with the financial support from the Ministry of
Education and Science of the Russian Federation in the framework of Increase Competitiveness
Program of NUST «MISiS» (grant no. К1-2015-045). Authors A. Karmakar and A. Paul express their
gratitude to the FCT for post-doctoral fellowships (Ref. No. SFRH/BPD/76192/2011 and
SFRH/BPD/88450/2012). SACC also thanks FCT for Investigador FCT program
(IF/01381/2013/CP1160/CT0007), with financing from the European Social Fund and the Human
Potential Operational Program. This work was supported by Project POCI-01-0145-FEDER-006984—
Associate Laboratory LSRE-LCM funded by FEDER through COMPETE2020—Programa Operacional
Competitividade e Internacionalização (POCI)—and by national funds through FCT.
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Dalton Transactions
Page 16 of 16
View Article Online
DOI: 10.1039/C7DT01056G
Lanthanide Metal Organic Frameworks based on dicarboxyl-
functionalized arylhydrazone of barbituric acid: Syntheses,
Structures, Luminescence and Catalytic Aldehydes Cyanosilylation
a
a
a
a
Anirban Karmakar *, Guilherme M. D. M. Rúbio , Anup Paul , M. Fátima C. Guedes da Silva ,
a,d
b,c
e
Kamran T. Mahmudov , Firudin I. Guseinov , Sónia A.C. Carabineiro and Armando J. L.
a
Pombeiro *
a
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais,
1
049–001, Lisbon, Portugal. E-mail: anirbanchem@gmail.com; pombeiro@tecnico.ulisboa.pt.
b
Department of Chemistry, M. V. Lomonosov Moscow State University, 1 Leninskie Gory, 119992
Moscow, Russian Federation.
c
National University of Science and Technology «MISIS», Moscow Leninsky prosp. 4, 119049
Moscow, Russian Federation.
d
Department of Ecology and Soil Sciences, Baku State University, Z. Xalilov Str. 23, Az 1148 Baku,
Azerbaijan.
e
Laboratório de Catálise e Materiais, Laboratório Associado LSRE-LCM, Faculdade de Engenharia,
Universidade do Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto, Portugal.
Metal organic frameworks of Ln(III) act as recyclable heterogeneous catalysts for cyanosilylation of
aldehydes under solvent-free conditions.