Zinc(II) and Copper(II) Metal–Organic Frameworks Constructed from a Terphenyl-4,4′′-dicarboxylic Acid Derivative: Synthesis, Structure, and Catalytic Application in the Cyanosilylation of Aldehydes

Article abstract of DOI:10.1002/ejic.201600902

Solvothermal reaction of zinc(II) and copper(II) salts with 3,3′′-dipropoxy-[1,1′:4′,1′′-terphenyl]-4,4′′-dicarboxylic acid (H₂L) gave rise to the 1D and 2D metal–organic frameworks (MOFs) [Zn(L)(dmf)₂]_n(1), [Zn₂

Full text of DOI:10.1002/ejic.201600902

A Journal of
Accepted Article
Title: Zn(II) and Cu(II) Metal Organic Frameworks Constructed from Terphenyl-4,4´´-
dicarboxylic Acid Derivative: Synthesis, Structure and Catalytic Application in
Aldehyde Cyanosilylation
´
Authors: ANIRBAN KARMAKAR; Anup Paul; Guilherme M. D. M. Ru´bio; M. Fatima
C. Guedes Da Silva; Armando J.L. Pombeiro
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201600902
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European Journal of Inorganic Chemistry
10.1002/ejic.201600902
Zn(II) and Cu(II) Metal Organic Frameworks Constructed from
Terphenyl-4,4′′-dicarboxylic Acid Derivative: Synthesis, Structure
and Catalytic Application in Aldehyde Cyanosilylation
Anirban Karmakar*, Anup Paul, Guilherme M. D. M. Rúbio, M. Fátima C. Guedes da Silva* and
Armando J. L. Pombeiro*
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais,
1049–001, Lisbon, Portugal. E-mail: anirbanchem@gmail.com; fatima.guedes@tecnico.ulisboa.pt;
pombeiro@tecnico.ulisboa.pt.
Abstract
Solvothermal reaction of zinc(II) and copper(II) salts with 3,3''-dipropoxy-[1,1':4',1''-terphenyl]-4,4''-
dicarboxylic acid (H2L) gave rise to the 1D and 2D MOFs [Zn(L)(DMF)2]n (1), [Zn2(L)(NO3)2(4, 4’-
Bipyridine)2]n.n(DMF) (2), [Cu(L)(H2O)2]n.2n(H2O) (3) and [Cu3(OH)2(L)2]n.n(H2O) (4) which were
characterized by elemental analysis, FT-IR spectroscopy and X-ray single-crystal diffraction. 1 and 3
have a zig-zag and a linear type 1D structure, respectively, whereas 2 and 4 possess a rectangular
grid and a layer type 2D structure. In 2 and in 4, a dinuclear Zn(II) cluster (C2O4Zn2) or a trinuclear µ3-
hydroxo bridged Cu(II) cluster [Cu3(OH)2]n, respectively, acts as a building block unit. These
frameworks act as heterogeneous catalysts (the Zn-MOFs being more active than the Cu-MOFs, and
1 acting as the most efficient one) for the cyanosilylation reaction of aldehydes with trimethylsilyl
cyanide (TMSCN) at room temperature. These MOF-based heterogeneous catalysts are of easy
recovery and can be reused, at least for a few consecutive cycles, without losing activity.
Introduction
The design and synthesis of microporous metal–organic frameworks (MOFs) have become a subject
of extensive investigation due to their intriguing architectures and functional properties, namely in
gas storage and separation, catalysis, sensing, luminescence and drug delivery etc1. The applications
of such materials largely depend on the metal ions, linkers size, shape and other properties of the
frameworks2 and, e.g., a small change in ligand conformation can produce significant differences in
the final structure3.
In this context, rigid polycarboxylate ligands and their derivatives have been extensively utilized to
synthesize various MOFs due to their strong coordination ability in diverse modes, being able to
satisfy the geometric requirement of the metal centres leading to higher dimensional frameworks
and topologies4. Rigid aromatic carboxylic acid ligands, such as terphenyl-4,4′′-dicarboxylic acid5 and
a few substituted (methyl and methoxy) derivatives6 have received considerable attention for the
construction of interesting MOFs. The introduction of a flexible side functional arm, such as the
propoxy group, in terphenyl-4,4′′-dicarboxylic acid can influence the planarity of the ligand with a
considerable effect on the MOF structure and interpenetration.
In this context, we have selected 3,3''-dipropoxy-[1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid (H2L) as
an organic linker due to the following features: (a) the multiple coordination sites may generate
1
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European Journal of Inorganic Chemistry
10.1002/ejic.201600902
multidimensional structures; (b) this species contains side functional arms (propoxy groups) which
may affect the ligand conformation during the self-assembling process and also influence the
network topology. Thus, in the present work we aim to get an insight on how the conformational
preference, flexibility of side functional group and rigidity of the dicarboxylate framework could be
utilized in MOF synthesis.
Cyanosilylation is a fundamental carbon–carbon bond forming reaction in organic chemistry7, which
is used to synthesize, e.g., cyanohydrins which are key derivatives in the synthesis of fine chemicals
and pharmaceuticals8. Cyanohydrins are versatile organic compounds for both synthetic chemistry
and biological processes and can be transformed into a wide variety of important species such as α-
hydroxy acids, α-hydroxy aldehydes and β-aminoalcohols. For the preparation of cyanohydrins, the
use of a catalyst with a Lewis acid or base character, capable of activating both the substrate and the
cyanide precursor, is necessary, affording highly versatile cyanohydrin trimethylsilyl ethers. The most
commonly used cyanide source is trimethylsilyl cyanide (TMSCN). Cyanosilylation reactions have
been extensively studied in homogeneous media using discrete complexes and coordination
polymers containing various d-block,9 f-block10 and a few p-block11 metal ions, but only a few studies
have employed heterogeneous catalysts12. Recently, a few MOFs have been used for cyanosilylation
of aldehydes13, but the development of efficient MOF based catalysts (in particular heterogeneous
ones) is still an understudied subject that deserves to be explored.
Therefore, the general objectives of this study are the following: (i) design, preparation and
characterization of multi-dimensional MOFs using 3,3''-dipropoxy-[1,1':4',1''-terphenyl]-4,4''-
dicarboxylic acid (H2L) as a linker; (ii) investigation of the catalytic activity of the synthesized
complexes in the cyanosilylation reaction of aldehydes. In accord, by using H2L as a pro-ligand, we
report the preparation and characterization of four different 1D and 2D polymers, viz. [Zn(L)(DMF)2]n
(1), [Zn2(L)(NO3)2(4, 4’-Bipyridine)2]n.n(DMF) (2), [Cu(L)(H2O)2]n.2n(H2O) (3) and [Cu3(OH)2(L)2]n.n(H2O)
(4), and their heterogeneous catalytic activities towards the cyanosilylation reaction of aldehydes
with TMSCN (trimethylsilyl cyanide).
Results and Discussion
Syntheses and characterization
The pro-ligand 3,3''-dipropoxy-[1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid (H2L) was synthesised via
Pd-mediated cross-coupling reactions between methyl 4-iodo-2-propoxybenzoate and 1,4-bis(5,5-
dimethyl-1,3,2-dioxaborinan-2-yl)benzene by following the reported procedure14a,b and subsequent
hydrolysis with excess of KOH (Scheme 1). The solvothermal reaction of Zn(NO3)2.6H2O or
Cu(NO3)2.3H2O with H2L in DMF:MeOH or DMF:MeOH:H2O led to the formation of the MOFs
[Zn(L)(DMF)2]n (1), [Zn2(L)(NO3)2(4,4’-Bipyridine)2]n.n(DMF) (2), [Cu(L)(H2O)2]n.2n(H2O) (3) and
[Cu3(OH)2(L)2]n.n(H2O) (4), respectively (Scheme 1).
H2L and the synthesised complexes 1-4 were characterised by elemental analyses, FT-IR and
multinuclear (1H and 13C only in the case of H2L in view of the non-solubility of the MOFs) NMR
techniques, and single crystal X-ray diffraction analysis (in the case of MOFs). The 1H NMR spectrum
of H2L exhibits characteristic resonances owing to –COOH at δ 12.55 and to the alkoxy chain -O-CH3-
CH2-CH3 attached to the aromatic ring which exhibits the resonances due to –CH3, -CH3-CH2- and –O-
CH2- protons at δ 1.04, 1.79 and 4.15, respectively (Fig. S7). Resonances due to phenyl ring protons
2
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European Journal of Inorganic Chemistry
10.1002/ejic.201600902
are observed in the range of δ 7.39-7.86. In its 13C NMR spectrum, the signals due to –COOH, -O–
CH2-, CH3-CH2- and -CH3 appear at δ 167.7, 70.28, 22.36 and 10.68, respectively, along with other
resonances at their usual positions (Fig. S8).
Scheme 1. Syntheses of ligand H2L and MOFs 1-4.
In the IR spectra of 1-4, the characteristic strong bands of the coordinated carboxylate
groups appear at 1609–1600 cm-1 for the asymmetric stretching and 1384-1391 cm-1 for the
symmetric one14c. The C–O stretching of coordinated carboxylate group is observed between 1215
and 1224 cm-1. A medium broad band between 2963 and 2967 cm-1 is due to νCH of the propoxy
groups. For H2L, the strong band at 1685 cm-1 is due to νCO of uncoordinated carboxylic acid groups,
whereas νCH of the aliphatic groups appears at 2966 cm-1.
Crystal structure analyses
According to the crystal structure analyses, 1-4 crystallize in different space groups (1 in C2/c, 2 and
3 in P-1 and 4 in P21/n). Compounds 1 and 3 have zig-zag and linear type one dimensional structure,
respectively, while compounds 2 and 4 possess a rectangular grid and layer type 2D structure.
Selected bond distances and angles of 1 are listed in Table S3 (supporting information).
Compound 1 comprises one Zn2+ ions, one L2- ligand and two coordinated dimethylformamide
molecules (Figures 1A and 1B) and features a zig-zag type one-dimensional coordination polymeric
chain (Figure 1C) which expands to 2D by means of H-bond interactions (Figure 1D). The Zn1 center
presents a distorted octahedral environment and binds to four carboxylate oxygen atoms of two
neighboring L2- units in a chelating bidentate fashion [Zn1–O1, 2.1861(13) Å and Zn1–O2, 2.1200(11)
Å]. The remaining two coordination sites of zinc are engaged to two oxygen atoms from two DMF
molecules [Zn1–O4, 2.0771(13) Å] which are displayed in mutual cis position. The two carboxylate
groups are coordinated to the Zn(II) center almost in perpendicular fashion (dihedral angle between
3
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European Journal of Inorganic Chemistry
10.1002/ejic.201600902
the two binding COO- groups of 74.92o). The L2- ligand is not planar; the carboxylate containing
phenyl groups (C2-C7 and C8-C10) make angles of 32.04o with the central phenyl ring. In addition,
the angle between the least-square planes of the carboxylate moiety and the attached phenyl group
is of 33.93 o. The two propoxy arms (-OCH2CH2CH3) are oriented in opposite direction with CphenylOCC
torsion angles of 172.75o. In a chain of 1 the metal cations are 19.23 Å apart and the shortest
intermolecular ZnZn distance equals the unit cell b dimension (7.5333 Å).
A
B
C
D
Figure 1: (A) The molecular structure of framework 1 with partial atom labelling scheme. Symmetry
codes to generate equivalent atoms: ‘) 1-x, y, 1/2-z. (B) Schematic representation of 1. (C) One
dimensional structure of 1. (D) A packing view of framework 1.
The hydrothermal reaction of 3,3''-dipropoxy-[1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid (H2L) with
zinc (II) nitrate hexahydrate in presence of 4, 4’-bipyridine as auxiliary ligand led to the formation of
a two dimensional network [Zn2(L)(NO3)2(4, 4’-Bipyridine)2]n .n(DMF) (2) (Figure 2B). Single-crystal X-
ray diffraction analysis disclose that the asymmetric unit of 2 contains one Zn2+ ions, half a L2- ligand,
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European Journal of Inorganic Chemistry
10.1002/ejic.201600902
one chelating nitrate anion, one coordinated 4, 4’-bipyridine molecule and one non-coordinated
DMF molecule (Figures 2A and 2D). The Zn1 ion has a distorted octahedral geometry with its
equatorial plane occupied by one of the O-carboxylate atoms from two neighboring L2- ligand [Zn1-
O1, 2.010(4) Å and Zn1-O2, 2.004(5) Å] and two O-atom of the chelating nitrate anion [Zn1-O4, 2.294(6) Å
and Zn1-O5, 2.238(6) Å], whereas the axial sites are occupied by the N-atoms from two 4, 4’-bipyridine
molecules [Zn1-N1, 2.142(5) Å and Zn1-N2, 2.165(5) Å]. In this framework the carboxylate groups are
bound in a syn-syn bridigning bidentate fashion thus giving rise to a dinuclear C2O4Zn2 cluster which
acts as a secondary building block (Figure 3B) where each of these unit is associated with two L2-
ligands, four 4, 4’-bipyridine molecules and two nitrate anions. The minimum Zn···Zn distance
reaches 3.770(2) Å. The L2- ligand is also not planar, the carboxylate containing rings being twisted
22.35o from the central phenyl group, and the dihedral angle between the carboxylate group and the
attached phenyl is of 58.42o. The two propoxy arms are oriented in opposite direction but the
CphenylOCC torsion angles are now much shorter (64.91o).
A
B
C
D
Figure 2: The molecular structure of 2 with partial atom labelling scheme (hydrogen atoms are
omitted for clarity) (A), and its schematic representation (B). Two dimensional arrangement of
framework 2 showing the open rectangular channels emptied (C), and with encapsulated DMF
molecules indicate as space fill model (D).
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European Journal of Inorganic Chemistry
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The 2D polymeric architecture of 2 also has open rectangular channels with approximate dimension
of 11.4 x 19.4 Å2, which are occupied by the DMF molecules (Figure 2D).
A
B
C
Figure 3. Schematic representation of the asymmetric unit of 3 (A), its one dimensional structure (B)
and two dimensional hydrogen bonded packing view (C). Symmetry codes to generate equivalent
atoms: B: ‘) -x, 2-y, 1-z; C: ‘) -x, 1-y, 1-z.
The single crystal analysis of 3 (Figure 3) reveals a linear 1D framework constructed from Cu(II) ions,
one L2- ligands and two coordinated water molecules; the compound crystallized with two non-
coordinated water molecules. The Cu(II) centre displays a square planner geometry (τ4= 0)15a, with
two of the trans positions occupied by one of the O-atoms from L2- ligands [Cu1-O2 1.9659(19) Å]
and the remaining ones occupied by two water molecules [Cu1-O4 1.993(3) Å]. The Cu-Owater bond
distance is slightly larger than the Cu-Ocarboxylate bond distance. The planarity of the L2- ligand is
greater than that found for 1 and 2, as indicated by the angle of 15.34o between the least-square
planes of the carboxylate-containing and the central- phenyl rings. In contrast, the twisting of the
COO- moiety relative to the attached phenyl, assumes the highest value (50.60o). Additionally, the
propoxy substituents are nearly co-planar (CphenylOCC torsion angle of 175.82o).
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European Journal of Inorganic Chemistry
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The intermolecular organization in 3 is characterized by extensive hydrogen bond interactions. The
carboxylate O1- and the propoxy-O3 atoms act as acceptors from the coordinated water molecules
leading to the expansion of the 1D chains to a 2D hydrogen bonded network (Figure 3B). Such
interactions are further reinforced by contacts linking the non-coordinated O5-water molecule with
the carboxylate O1-atoms of vicinal chains, thus forming a close square with graph set (8)15b [O5-
H5A·····O1, dD–A 2.850(4) Å, <D–H····A 158.5o; O5-H5B·····O1, dD–A 2.872(5) Å, <D–H····A 151.7o]. Other
strengthening contacts comprise the O6-water molecule which simultaneously binds the O5-water
molecule and the O2-carboxylate atom [O6-H6B·····O5, dD–A 2.902(5) Å, <D–H····A 155.3o; O6-
H5A·····O2, dD–A 2.989(4) Å, <D–H····A 161.7o].
The use of Cu(II) salts for coordination polymerization with H2L in the presence of DMF, 1,4-dioxane
and water has led to a unique structure (4) in which the Cu2+ ions aggregate via Ohydroxo , Oaqua and
Ocarboxylate atoms into one-dimensional chains, which are doubly crosslinked with deprotonated ligand
(L2-) giving rise to a two-dimensional framework (Figure 4C). In 4, the asymmetric unit contains three
Cu2+ ion, two deprotonated ligands (L2-), two hydroxo anions, two coordinated water molecules and
one non-coordinated water molecule (Figure 4A). The three crystallographically independent Cu(II)
ions have distorted square pyramidal geometry (τ5 = 0.21, 0.06 and 0.07 for Cu1, Cu2 and Cu3,
respectively)15b. They are interconnected with each other via µ3-hydroxo and µ2-carboxylate bridged
(Figure 4B). The coordination sphere of each metal centres formed by two carboxylate oxygen atom
of a L2- unit and two O-atoms from hydroxo anion, which occupies four of the equatorial sites. The
axial position is occupied by other carboxylate oxygen. As expected and due to Jahn–Teller
distortion16 the axial Cu-O bond distance is slightly larger [Cu1–O11, 2.615(4) Å; Cu2–O2, 2.564(4) Å;
Cu3–O7, 2.511(4) Å] than the equatorial ones.
A
B
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European Journal of Inorganic Chemistry
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C
Figure 4: Schematic representation of 4 (A); One dimensional chain of Cu(II) ions bridged by hydroxo
and carboxylate anions in the framework 4 (B); Two dimensional polymeric structure of framework 4
(C). Symmetry codes to generate equivalent atoms: B: ‘) -x, 1-y, 1-z.
The shortest interatomic distances between the copper ions along the polymeric copper-oxygen
cluster are of 2.9651 or 3.0297 Å, involving symmetry related Cu3 or Cu2 cations, followed by 3.0796
Å and concerning a Cu1⋯Cu3 length. While the hydroxo anion O14 bridges two Cu2 leading to a 4-
membered Cu2O2 ring (Cu-O-Cu angle of 99.6o), and additionally to a Cu1 centre, the O15-hydroxo
make similar connections but between Cu3 (forming the 4-membered Cu2O2 core with Cu-O-Cu
angle of 97.9o) and then to the cited Cu1. The angle between the least-square planes of those four
membered rings is of 18.30o, and they are 1.710 and 1.627 Å apart from the common Cu1 cation,
respectively.
One of the doubly deprotonated ligand (L2-) is interconnected with four different copper ions and
one of carboxylate arms are coordinated with two Cu(II) centers (Cu1 and Cu3) via a µ2–η1–η1-
bridging mode, while the another part of the ligand are connected with other two copper (Cu1’ and
Cu3’) ions in a µ2–η1–η0-bridging fashion. However other ligand coordinated with three Cu(II) centres
and for this one carboxylate coordinated with two Cu(II) centers (Cu1 and Cu2) via a µ2–η1–η1-
bridging mode and other carboxylate group coordinated to the Cu2 centre in monodentate fashion.
In this framework a trinuclear µ3-hydroxo bridged Cu(II) cluster [Cu3(OH)2] act as a building blocks
unit which are forming a one dimensional chain and these 1D chains are further connected via
doubly deprotonated ligands to forming a two-dimensional architecture (Figure 4C).
To improve the description of the crystal structures of 1-4 we performed their topological analysis by
reducing their multidimensional structures to simple node-and-linker nets where the metallic nodes
and the organic linkers represent secondary building units (SBUs). We have carried out these
analyses by using TOPOS 4.0.17 Topological analysis of frameworks 1 and 3 reveals that they have a
2-connected uninodal net with a topological type 2C1 net (Figure 5A and 5C). In the particular case
of 2, to represent the simplified net structure of this framework we consider dinuclear Zn(II) unit as a
single node which subsequently coordinated via 2 different carboxylate linkers and four 4,4’-
bipyridine. Each ligand as well as 4, 4’-bipyridine are connected with two different metal and acts as
a 2-connected nodes. The polymeric chain structure thus generated is a 2, 2, 6-connected trinodal
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European Journal of Inorganic Chemistry
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net (Figure 5B). However, the 2D framework 4 has more complex 3,3,4,4,4,5,5-connected 7-nodal
network topology (Figure 5D).
A
B
C
D
Figure 5 Node-and-linker-type descriptions of: (A) 1D zig-zag MOF of 1; (B) the 2D coordination
frameworks in 2; (C) the 1D linear type coordination framework in 3; (D) the 2D coordination
frameworks in 4. The zinc nodes are represented in green whereas the copper nodes are in blue
color, the carboxylate linker in red, the 4,4’-bipyridine are in pink and the hydroxyl groups are in
yellow colour.
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Catalysis
We have tested the activity of the synthesized frameworks (1-4) as solid heterogeneous catalysts in
the cyanosilylation reaction of various aldehydes, namely 4-nitrobenzaldehyde as a model substrate,
and performed the cyanosilylation reaction by using a mixture of aldehyde, trimethylsilyl cyanide
and a Zn or Cu-catalyst in CH2Cl2 (DCM) at room temperature (Scheme 2, Table 1).
Scheme 2
When framework 1 is used as catalyst (2 mol%), a high conversion of 94% of 4-nitrobenzaldehyde
into 2-(4-nitrophenyl)-2-((trimethylsilyl)oxy)acetonitrile is reached after 10
h reaction in
dichloromethane, at room temperature (entry 6, Table 1). However, with frameworks 2, 3 and 4,
lower conversions of 85%, 79% and 65% were obtained, respectively (entries 13-15, Table 1). The
plot of yield vs. time (until 10 h) for the cyanosilylation reaction of 4-nitrobenzaldehyde with TMSCN
and 1 in DCM is presented in Fig. 6A. Upon further extending the reaction time to 24 h, only a slight
increase of the product yield to 96% occurred. Moreover, no other products were detected and the
yield of this product is considered to be the conversion of 4-nitrobenzaldehyde.
The four MOFs activities follow the order of 1 > 2 > 3 > 4, showing that the Zn(II) MOFs are more
active than the Cu(II) ones. Although a relationship between structure and catalytic activity in the
present study cannot be clearly established, the highest conversation shown by the compound 1
may eventually be associated to its 1D zig-zag structure or favourable packing arrangement for easily
accessible metal centres, together with the higher Lewis acidity of the zinc sites.
Table 1 Optimization of the parameters of the cyanosilylation reaction between 4-nitrobenzaldehyde and
trimethylsilyl cyanide (TMSCN) with Zn- and Cu-MOF as catalystsa
Entry
Catalyst
Time (h)
Amount of
Solvent
Yieldb (%)
TONc
Catalyst (mol%)
1
1
1
1
1
1
1
1
2
4
6
8
2.0
2.0
2.0
2.0
2.0
2.0
DCM
DCM
DCM
DCM
DCM
DCM
32
61
72
81
87
94
16
30
36
40
43
47
2
3
4
5
6
10
7
8
1
1
10
10
1.0
5.0
DCM
DCM
75
95
75
19
9
1
1
1
1
10
10
10
10
2.0
2.0
2.0
2.0
CH3CN
THF
CHCl3
MeOH
82
73
90
87
41
36
45
43
10
11
12
10
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European Journal of Inorganic Chemistry
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13
14
15
2
3
4
10
10
10
2.0
2.0
2.0
DCM
DCM
DCM
85
79
65
42
39
32
16
17
18
19
Blank
Zn(NO3)2.6H2O
Cu(NO3)2.3H2O
10
10
10
10
-
DCM
DCM
DCM
DCM
12
18
16
13
-
9
8
-
2.0
2.0
2.0
H2L
aReaction conditions: 4-nitrobenzaldehyde (0.50 mmol), trimethylsilyl cyanide (1.0 mmol), 2.0 mol%
b
1
of catalyst 1 and solvent (DCM) (2.0 mL), at room temperature.; Calculated by H-NMR as the
number of moles of product 2-(4-nitrophenyl)-2-((trimethylsilyl)oxy)acetonitrile per mole of
c
aldehyde X 100; Number of moles of product 2-(4-nitrophenyl)-2-((trimethylsilyl)oxy)acetonitrile
per mole of catalyst.
We have also tested the effect of catalyst amount and solvents in the cyanosilylation reaction
catalysed by 1. The increase of the catalyst amount from 1.0 to 2.0 mol% enhances the product yield
from 75 to 94%, respectively (entries 7 and 6, Table 1), but a further increase of that amount (up to
5%) results only in an insignificant yield improvement of 1% (entry 8, Table 1), with a marked
decrease of the TON value. We have also checked the catalytic reaction in various solvents, such as
CH3CN, THF, CHCl3, MeOH and CH2Cl2, and the results indicate that CH2Cl2 (94% yield) is the best one
for such a transformation, whereas the worst one is THF (73% yield) (entries 9-12, Table 1).
A
B
Figure 6 (A) Plot of 2-(4-nitrophenyl)-2-((trimethylsilyl)oxy)acetonitrile yield vs. time for the
cyanosilylation reaction, catalyzed by 1, of 4-nitrobenzaldehyde with TMSCN at room temperature
(dotted line concerns the catalyst removal after 2 h: see text). (B) Effect of the catalyst recycling on
the yield of 2-(4-nitrophenyl)-2-((trimethylsilyl)oxy)acetonitrile.
A blank test was carried out with 4-nitrobenzaldehyde in the absence of any catalyst at room
temperature and only 12% of conversion detected after a reaction time of 10 h. We have also
checked the reactivity of Zn(NO3)2.6H2O, Cu(NO3)2.3H2O and free ligand (H2L) in CH2Cl2 and the
obtained reaction yields are only 18%, 16% and 13%, respectively (entries 16-18, Table 1).
We have also compared the activities of catalyst 1 in the reactions of other substituted aromatic and
aliphatic aldehydes with trimethylsilyl cyanide, producing the corresponding cyanohydrin derivatives
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with yields ranging from 65 to 91% (Table 2). Aryl aldehydes bearing strong electron-withdrawing
substituents (nitro and chloro) exhibit the highest reactivities (entries 2 and 3, Table 2), that may be
related with an increase of the electrophilicity of the substrate. The aldehydes containing electron-
donating groups (methyl or methoxy) show lower reaction yields (entries 5 and 6, Table 2), as
expected. The ortho-substituted aldehyde shows a lower reactivity possibly due to steric hindrance.
The aliphatic aldehydes give good reaction yields in the 84-88% range (entries 9 and 10, Table 2).
Table 2: Cyanosilylation reaction between various aldehydes and trimethylsilyl cyanide with catalyst 1a
Entry
Reactant
Product
Yieldb(%)
TONc
Benzaldehyde
3-nitrobenzaldehyde
4-chlorobenzaldehyde
4-hydroxybenzaldehyde
4-methylbenzaldehyde
4-methoxybenzaldehyde
2-nitrobenzaldehyde
Salicylaldehyde
2-phenyl-2-((trimethylsilyl)oxy)acetonitrile
2-(3-nitrophenyl)-2-((trimethylsilyl)oxy)acetonitrile
2-(4-chlorophenyl)-2-((trimethylsilyl)oxy)acetonitrile
2-(4-hydroxyphenyl)-2-((trimethylsilyl)oxy)acetonitrile
2-(p-tolyl)-2-((trimethylsilyl)oxy)acetonitrile
2-(4-methoxyphenyl)-2-((trimethylsilyl)oxy)acetonitrile
2-(2-nitrophenyl)-2-((trimethylsilyl)oxy)acetonitrile
2-(2-hydroxyphenyl)-2-((trimethylsilyl)oxy)acetonitrile
2-((trimethylsilyl)oxy)propanenitrile
1
2
3
4
5
6
7
8
9
74
91
86
81
71
65
83
63
88
84
37
45
43
40
35
32
41
31
44
42
Acetaldehyde
Propionaldehyde
2-((trimethylsilyl)oxy)butanenitrile
10
a
Reaction conditions: 2.0 mol% of catalyst 1, solvent (CH2Cl2) (2.0 mL), trimethylsilyl cyanide (1.0
mmol) and aldehyde (0.50 mmol) for 10 h at room temperature; b Calculated by 1H NMR; c Number of
moles of product per mole of catalyst.
We have performed a competition cyanosilylation reaction in the presence of 1 involving equal
molar amounts of 3-nitrobenzaldehyde and acetaldehyde, substrates with a marked difference in
size, and a higher product yield was observed in the former case, as when using them separately.
Moreover, within aliphatic aldehydes, no substantial yield decrease was observed with the increase
of the substrate size. Hence, the catalysis does not appear to be mainly occurring within the MOF
pores.
In order to examine the stability of 1 in the cyanosilylation reaction, we have tested the recyclability
of this heterogeneous catalyst. 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 1 and the catalytic system
maintained the full activity for at least five consecutive cycles as shown in Fig. 6B.
To further clarify if the catalytic process is heterogeneous or homogeneous, the following test18 for
the cyanosilylation reaction was carried out. We performed a controlled experiment with catalyst 1
until an intermediate yield (ca. 62%) was observed (2 h), then removed the catalyst by centrifugation
and kept the catalyst-free reaction solution under the same conditions stirred for additional 10 h. As
shown in Fig. 6A (dotted line), after removal of the solid catalyst, the yield of 2-(4-nitrophenyl)-2-
((trimethylsilyl)oxy)acetonitrile did not increase significantly. These results demonstrate that the
catalysis is heterogeneous in nature. Additionally, the filtrated solution, after the separation of the
catalyst, was evaporated to dryness and the amount of zinc determined was only 0.025% of the
amount used in the reaction, thus ruling out any significant leaching of the catalyst. In order to check
the structural integrity of the catalysts 1-4, we have performed FT-IR and powder X-ray diffraction
12
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European Journal of Inorganic Chemistry
10.1002/ejic.201600902
analyses of the catalyst before and after the catalysis reaction. They indicate that the structure of
the solid was retained (Figures S1-S4).
Our catalysts appear to be usually much more efficient for the aldehyde cyanosilylation than other
reported heterogeneous ones. In fact, for example, the zinc(II) MOFs of 1,2-bis(4-pyridyl)ethane lead
to overall yields of only 14-18% after 24 h reaction time in the cyanosilylation reaction of
benzaldehyde and TMSCN19a. Moreover, the use of 1D, 2D and 3D MOFs of Zn(II) based on 4,4’-
bipyridine and acetate, results into an yield of only 21-22%19b
.
In case of
a
Cu3(benzenetricarboxylate)2 MOF, an yield of 57% after 72 h was obtained19c. The 2D frameworks of
copper(II) constructed by Cu(II), 4,4’-bipyridine and formato or acetate ligands lead to an overall
yield of only 2% in the reaction of benzaldehyde and TMSCN for 5h19d. Besides that, a Ln-MOF, Tb-
tricarboxytriphenylamine MOF, in the reaction of 4-nitrobenzaldehyde and TMSCN, results into an
yield of 47% after 4 h reaction time19e. Recently, Huh et al. reported a 3D cadmium(II) MOF bearing
rigid 1,4-naphthalenedicarboxylate which catalyses the cyanosilylation of 4-nitrobenzaldehyde with
an overall yield of 49% after 72 h at 50oC19f. Moreover, incubation of benzaldehyde and TMSCN with
pristine CuBTC as the catalyst led to a conversion of 56.4% at 40oC for 48 h19g. Arriortua et al.
reported the heterometallic MOF [NaCu(2,4-HPdc)(2,4-Pdc)] (2,4-H2Pdc = pyridine-2,4-dicarboxylic
acid) which catalyses the cyanosilylation of benzaldehyde with an yield of 85% after 24 h under
solvent free conditions19h. Nevertheless, our catalyst 1 exhibits an yield of 94% for 4-
nitrobenzaldehyde cyanosilylation and 74% for benzaldehyde cyanosilylation, at room temperature.
Besides MOFs, other classes of catalysts, such as metal complexes, oxides, polyoxometalates and
nano materials, have been reported, which can give comparable yields for such a reaction. For
example,
a
mononuclear
copper(II)
complex
of
2-(2-(2,4-dioxopentan-3-
ylidene)hydrazinyl)benzenesulfonate and ethylenediamine leads to an overall yield of 85% after 16 h
reaction by using 5 mol% of catalyst in the cyanosilylation reaction of benzaldehyde and TMSCN19i. A
mononuclear Zn(II) complex with an amide-based ligand containing thiazole leads to an overall yield
of 90% in the reaction of benzaldehyde and TMSCN for 6 h by using 5 mol% of catalyst19j. A Ce(III)
complex of D-proline, in the reaction of benzaldehyde and TMSCN, results into an yield of 90% after
40 h19k. Moreover, cyanosilylation of benzaldehyde with TMSCN in the presence of nanocrystalline
magnesium oxide provides a reaction yield of 86% in 3 h19l. The Preyssler P5W30 polyoxometalate
based complex {[Cu12(pbtz)2(Hpbtz)2(OH)4(H2O)16][Na(H2O)P5W30O110]}·16H2O {H2pbtz = 5’-(pyridin-2-
yl)-1H,2’H-3,3’-bi(1,2,4-triazole)} catalyzes the cyanosilylation of benzaldehyde with TMSCN leading
to an overall yield of 62% after 24 h19m. A bifunctional catalyst derived from Ti(OiPr)4 and a N-oxide
ligand was applied to the asymmetric cyanosilylation of benzaldehyde and 78% yield was obtained
by using 5 mol% catalyst at -78°C19n. Moreover, activated ceria nanorods were also used to catalyse
the cyanosilylation of benzaldehyde and ca. 92% yield was obtained after 1.5 h19o. However, in those
systems, a longer reaction time or higher or lower (even negative) temperatures are required, what
can be considered as disadvantages in comparison with our system.
Conclusions
We synthesized and characterized four different metal organic frameworks, namely [Zn(L)(DMF)2]n
(1), [Zn2(L)(NO3)2(4, 4’-Bipyridine)2]n.n(DMF) (2), [Cu(L)(H2O)2]n.2n(H2O) (3) and [Cu3(OH)2(L)2]n.n(H2O)
(4), of Zn(II) and Cu(II) constructed from 3,3''-dipropoxy-[1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid
13
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European Journal of Inorganic Chemistry
10.1002/ejic.201600902
(H2L) under different solvothermal conditions. X-ray diffraction structural analyses revealed that the
compounds 1 and 3 have zig-zag and linear type 1D structures, respectively, whereas compounds 2
and 4 possess a rectangular grid and layer type 2D structure.
We have also shown that our synthesized MOFs act as heterogeneous catalysts towards the
cyanosilylation reaction of various aldehydes with TMSCN at room temperature. The Zn(II)-MOFs
show higher activity than the Cu(II) ones which may reflect the higher Lewis acidity of the former.
Among the four MOFs of this study, compound 1, with a 1D zig-zag structure, is the most active one,
conceivably on account of structural factors. We have also proved the heterogeneous character, the
stability and recyclability of the catalyst 1 and showed that it can be recycled at least five cycles
without losing activity. The above observations provide further evidence that simple MOFs can be
utilized as effective heterogeneous catalysts in important types of reactions, such as that of this
work.
Experimental
The synthetic work was performed at open air, while the metal organic frameworks were prepared
under hydrothermal conditions. All the chemicals were obtained from commercial sources and used
as received. The infrared spectra (4000–400 cm-1) 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. The 1H and 13C NMR spectra were recorded at ambient temperature on a Bruker
Avance II + 300 (UltraShieldTMMagnet) spectrometer operating at 300.130 and 75.468 MHz for
proton and carbon-13, respectively. The chemical shifts are reported in ppm using tetramethylsilane
as the internal reference; abbreviations: s = singlet, d = doublet, t = triplet, q = quartet. Carbon,
hydrogen and nitrogen elemental analyses were carried out by the Microanalytical Service of the
Instituto Superior Técnico. Electrospray mass spectra (ESI-MS) were run with an ion-trap instrument
(Varian 500-MS LC Ion Trap Mass Spectrometer) equipped with an electrospray ion source. For
electrospray ionization, the drying gas and flow rate were optimized according to the particular
sample with 35 p.s.i. nebulizer pressure. Scanning was performed from m/z 100 to 1200 in methanol
solution. The compounds were observed in the positive mode (capillary voltage = 80–105 V). Powder
X-ray diffraction (PXRD) was conducted in a D8 Advance Bruker AXS (Bragg Brentano geometry)
theta-2theta 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˚.
Synthesis of 3,3''-dipropoxy-[1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid (H2L)
The pro-ligand H2L was synthesised with a slight modification in the procedure reported earlier14a,b
.
The intermediates a and b used for the syntheses of H2L are described in the experimental section of
the supporting information (ESI).
Methyl 4-iodo-2-methoxybenzoate (a) was synthesised and added to the reaction mixture of b
(0.604 g, 2.0 mmol), [Pd(PPh3)4] (0.200 g, 0.20 mmol) and K2CO3 (2.0 g, 14.5 mmol) dissolved in DMF
(30 mL), and the system was heated to 90 ⁰C under N2 for 24 h. The reaction mixture was then
poured into ice cold water (600 mL). The brown precipitate thus formed was extracted with CH2Cl2,
the solution dried with Na2SO4 and evaporated to dryness using a rotary evaporator. The crude
14
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European Journal of Inorganic Chemistry
10.1002/ejic.201600902
brown product was further purified by using column choromatagraphy (ethyl acetate:hexane) to
obtain dimethyl 3,3''-dipropoxy-(1,1':4',1''-terphenyl)-4,4''-dicarboxylate as a white product in 55%
yield.
This product was then hydrolysed by dissolving it (300 mg, 0.7 mmol) in tetrahydrofuran (THF, 20
mL), followed by addition of 4% KOH (20 mL) and stirring at room temperature overnight. The
system was then reduced to ca. 10 mL, acidified to pH~1 with conc. HCl, and the white solid product
thus obtained was washed several times with water until neutral and air dried. Yield: 80%. FT-IR
(KBr, cm-1): 3445 (bm), 2966 (bs), 2877 (m), 1685 (s), 1606 (s), 1563 (w), 1443 (m), 1390 (bm), 1309
(bs), 1262 (m), 1221 (m), 1153 (w), 1098 (w), 1043 (w), 1009 (w), 974 (w), 824 (s), 780 (s), 691 (m). 1H
NMR (DMSO-d6, 300 MHz, δ ppm): 7.25 (d, 4H, Ar-H), 7.74 (s, 2H, Ar-H), 7.34-7.39 (m, 4H, Ar-H),
4.15 (t, 2H, O-CH2-CH2-CH3), 1.79 (m, 2H, O-CH2-CH2-CH3), 1.04 (t, 3H, O-CH2-CH2-CH3). 13C NMR
(DMSO-d6, 75.45 MHz, δ ppm): 167.71, 158.82, 144.61, 139.31, 132.11, 127.88, 119.28, 112.34,
70.28, 22.36, 10.68. ESI-MS: Calcd. for [(M + H)]+ : m/z 435.5, found 435.0. Anal. Calcd. for C26H26O6
(M = 434.48): C, 71.87; H, 6.03;; Found: C, 72.04; H, 6.15.
Synthesis of 1
A mixture of Zn(NO3)2.6H2O (29 mg, 0.10 mmol) and H2L (43 mg, 0.10 mmol) was dissolved in 4 mL of
DMF and methanol (1 : 2). To this reaction mixture we added 0.2 mL of 28% aqueous ammonia
solution and a white precipitate was obtained. The precipitate was dissolved upon further addition
of 0.3 mL of 28% aqueous ammonia solution. Then, the resulting mixture was sealed in an 8 mL glass
vessel and heated at 75 ˚C for 48 h. Subsequent gradual cooling to room temperature afforded
colorless crystals of 1. Yield: 64% (based on Zn). Anal. Calcd. for C32H38N2O8Zn (M = 644.03): C, 59.68;
H, 5.95; N, 4.35; Found: C, 59.02; H, 5.65; N, 4.05. FT-IR (KBr, cm-1): 3361 (bs), 2963 (m), 2875 (w),
1608 (s), 1386 (bs), 1306 (w), 1215 (s), 1162 (w), 1109 (m), 1044 (w), 1012 (w), 979 (w), 896 (m), 826
(s), 792 (s), 699 (w).
Synthesis of 2
A mixture of Zn(NO3)2.6H2O (29.0 mg, 0.10 mmol), H2L (43 mg, 0.10 mmol) and 4,4’-bipyridine (31
mg, 0.20 mmol) was dissolved in 5 mL of DMF, methanol and water (1 : 4: 0.1) mixture. Then, the
resulting mixture was transferred to an 8 mL glass vessel and the sealed vessel was heated at 70 ˚C
for 48 h. It was subsequently cooled to room temperature, affording block-like colorless crystals of 2.
Yield: 42% (based on Zn). Anal. Calcd. for C26H27N4O7Zn (M = 572.88): C, 54.51; H, 4.75; N, 9.78; Found:
C, 54.11; H, 4.31; N, 9.45. FT-IR (KBr, cm-1): 3365 (bs), 2966 (m), 2874 (w), 1609 (s), 1532 (s), 1391 (s),
1327 (m), 1304 (w), 1217 (s), 1165 (w), 1047 (m), 1018 (w), 973 (m), 900 (w), 827 (s), 798 (s), 700
(m), 681 (w).
Synthesis of 3
Similarly, a mixture of Cu(NO3)2.3H2O (23.0 mg, 0.10 mmol) and H2L (43 mg, 0.10 mmol) was
dissolved in 4 mL of DMF, ethanol and water (1 : 4: 0.1) mixture. The resulting mixture was sealed in
an 8 mL glass vessel and heated at 75 ˚C for 48 h. It was subsequently cooled to room temperature,
affording plate-like green crystals of 3. Yield: 68% (based on Cu). Anal. Calcd. for C26H36CuO12 (M =
604.09): C, 51.69; H, 6.01. Found: C, 51.53; H, 6.32. FT-IR (KBr, cm-1): 3435 (bs), 2965 (m), 2877 (w),
1609 (s), 1473 (m), 1384 (bs), 1312 (w), 1224 (s), 1162 (w), 1113 (m), 1075 (w), 1042 (w), 1018 (m),
896 (m), 820 (s), 795 (m), 700 (w), 643 (m).
15
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European Journal of Inorganic Chemistry
10.1002/ejic.201600902
Synthesis of 4
A mixture of Cu(NO3)2.3H2O (23.0 mg, 0.10 mmol) and H2L (43 mg, 0.10 mmol) was dissolved in 5 mL
of DMF, 1,4-dioxane and water (1 : 4: 0.1) mixture. To this reaction mixture we added 0.01 mL of
concentrated HCl solution. The resulting mixture was sealed in an 8 mL glass vessel and heated at 85
˚C for 48 h. It was subsequently cooled to room temperature, affording green crystals of 4. Yield:
42% (based on Cu). Anal. Calcd. for C52H48Cu3 O17 (M = 1135.52): C, 55.00; H, 4.26. Found: C, 55.38; H,
4.01. FT-IR (KBr, cm-1): 3546 (s), 3436 (bs), 2967 (m), 2879 (w), 1600 (s), 1420 (s), 1385 (s), 1341 (s),
1223 (w), 1113 (w), 1047 (m), 867 (m), 786 (s), 687 (s).
Procedure for cyanosilylation reaction of aldehydes
A suspension of an aromatic aldehyde (0.50 mmol), trimethylsilyl cyanide (1.0 mmol) and 2 mol%
catalyst (6.5 mg for 1, 5.7 mg of 2, 6.0 mg of 3 and 11.3 mg of 4) in dichloromethane (2.0 mL) was
stirred at room temperature. After the desired time, the catalyst was removed by centrifugation.
After evaporation of solvent from the filtrate in a rotary evaporator, a crude solid was obtained. This
was dissolved in CDCl3 and analyzed by 1H NMR (supporting information, Fig. S6).
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 (1-4). 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
parameters were retrieved using Bruker SMART20 software and refined using Bruker SAINT20a on all
the observed reflections. Absorption corrections were applied using SADABS20a. Structures were
solved by direct methods by using the SHELXS-97 package20b and refined with SHELXL-9720b
.
Calculations were performed using the WinGX System–Version 1.80.0320c. The hydrogen atoms
attached to carbon atoms and to the 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 nitrogen atoms or the carbon atoms for phenyl and methylene
residues, and 1.5 Ueq of the parent carbon atoms for the methyl groups. The hydrogen atoms of
coordinated water molecules were located from the final difference Fourier map and the isotropic
thermal parameters were set at 1.5 times the average thermal parameters of the belonging oxygen
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 1481724-1481727 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.
16
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European Journal of Inorganic Chemistry
10.1002/ejic.201600902
Acknowledgements
This work has been supported by the Foundation for Science and Technology (FCT) (project
UID/QUI/00100/2013), Portugal. 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). The
authors acknowledge the Portuguese NMR Network (IST-UL Centre) for access to the NMR facility.
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Graphical Abstract
Zn(II) and Cu(II) Metal Organic Frameworks Constructed from
Terphenyl-4,4′′-dicarboxylic Acid Derivative: Synthesis, Structure
and Catalytic Application in Aldehyde Cyanosilylation
Anirban Karmakar*, Anup Paul, Guilherme M. D. M. Rúbio, M. Fátima C. Guedes da Silva* and
Armando J. L. Pombeiro*
a Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais,
1049–001, Lisbon, Portugal. E-mail: anirbanchem@gmail.com; fatima.guedes@tecnico.ulisboa.pt;
pombeiro@tecnico.ulisboa.pt.
Metal organic frameworks of Zn(II) and Cu(II) act as recyclable heterogeneous catalysts for
cyanosilylation reaction of aldehydes at room temperature.
21
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