Cluster-organic framework materials as heterogeneous catalysts for high efficient addition reaction of diethylzinc to aromatic aldehydes

Article abstract of DOI:10.1021/cm302953x

To explore the catalytic activity of heterometallic cluster-organic frameworks, three 3d-3d heterometallic cluster-organic frameworks based on the cooperative assembly of tetrahedral Cu₄I₄ and metal-carboxylate clusters with potential open metal sites were synthesized and described in detail. The structure of 1 consists of tetrahedral [Cu ₄I₄(INA)₄]^4- metalloligands (INA = isonicotinate) linking unusual Zn₈(μ₄-O)(COO) ₁₂(H₂O)₄ clusters into a (4,12)-connected network. Compound 2 features a 2-fold interpenetrating 4-connected bbf-type framework based on new [Cu₄I₄(INA)₂(DBO) ₂]^2- metalloligands (DBO = 1,4-diazabicyclo[2.2.2]octane) and paddle-wheel Zn₂(COO)₄ units. The 2-fold interpenetrating diamond-type framework 3 is constructed from tetrahedral [Cu₄I₄(INA)₄]^4- metalloligand and Mn₂(COO)₄(H₂O)₂(DMF) unit with potential open Mn centers. All three framework materials have notable catalytic activity on the diethylzinc addition to aromatic aldehydes, and the catalytic properties of compound 1 have been studied in detail. The results reveal that the heterogeneous catalysis of the diethylzinc addition to aromatic aldehydes by using cluster-organic framework as catalyst is determined by several experimental factors, such as temperature, reaction time, and the incorporation of electron-withdrawing groups in aromatic aldehydes.

Full text of DOI:10.1021/cm302953x

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Article
Cluster-Organic Framework Materials as Heterogeneous Catalysts for
High Efficient Addition Reaction of Diethylzinc to Aromatic aldehydes
Yan-Xi Tan, Yan-Ping He, and Jian Zhang
Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/cm302953x • Publication Date (Web): 27 Nov 2012
Downloaded from http://pubs.acs.org on November 30, 2012
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ClusterꢀOrganic Framework Materials as Heterogeneous Catalysts for High
Efficient Addition Reaction of Diethylzinc to Aromatic aldehydes
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YanꢀXi Tan, YanꢀPing He and Jian Zhang*
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State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter,
Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China.
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Eꢀmail: zhj@fjirsm.ac.cn
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RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required
according to the journal that you are submitting your paper to)
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ABSTRACT: To explore the catalytic activity of heterometallic clusterꢀorganic frameworks, three 3dꢀ3d
heterometallic clusterꢀorganic frameworks based on the cooperative assembly of tetrahedral Cu4I4 and
metalꢀcarboxylate clusters with potential open metal sites were synthesized and described in detail. The
structure of 1 consists of tetrahedral [Cu4I4(INA)4]4ꢀ metalloligands (INA = isonicotinate) linking
unusual Zn8(ꢁ4ꢀO)(COO)12(H2O)4 clusters into a (4,12)ꢀconnected network. Compound 2 features a 2ꢀ
fold interpenetrating 4ꢀconnected bbfꢀtype framework based on new [Cu4I4(INA)2(DBO)2]2ꢀ
metalloligands (DBO = 1,4ꢀdiazabicyclo[2.2.2]octane) and paddleꢀwheel Zn2(COO)4 units. The 2ꢀfold
interpenetrating diamondꢀtype framework 3 is constructed from tetrahedral [Cu4I4(INA)4]4ꢀ
metalloligand and Mn2(COO)4(H2O)2(DMF) unit with potential open Mn centers. All three framework
materials have notable catalytic activity on the diethylzinc addition to aromatic aldehydes, and the
catalytic properties of compound 1 have been studied in detail. The results reveal that the heterogeneous
catalysis of the diethylzinc addition to aromatic aldehydes by using clusterꢀorganic framework as
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catalyst is determined by several experimental factors, such as temperature, reaction time and the
incorporation of electronꢀwithdrawing groups in aromatic aldehydes.
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Keywords: Metalꢀorganic framework; Catalysis; Crystal structure; Cluster; Additional reaction
Introduction
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Metalꢀorganic frameworks (MOFs) or porous coordination polymers (PCPs) are receiving increasing
attention because of their potential applications in the areas of separation, heterogeneous catalysis, ion
exchange and gas storage.1ꢀ4 With large internal surface areas and uniform pore and cavity sizes, MOFs
share some of the catalytically relevant features of inorganic zeolites. Although MOFꢀbased catalysis has
become a hot topic in recent years, it is still in an immature phase and many detailed catalytic
mechanisms are worthy of further exploration.5
One promising point for MOFꢀbased catalysis is the presence of active metal centers in the structure.
For example, the catalytic activity of the wellꢀknown HKUSTꢀ1 and MILꢀ101 in the cyanosilylation of
benzaldehyde was due to the well defined accessible Lewis acidic sites exposed to the inner surface.6
Therefore, how to give birth to accessible active metal centers may be extremely challenging. An
effective approach is to construct inorganic building blocks with possible unsaturated coordination sites,
typically like the paddleꢀwheel Cu2(COO)4 unit combined with terminal molecules, the removal of
which leads to active metal sites.6 Another effective approach is to incorporate catalytic active metal
sites into organic ligands, such as metalloporphyrins and other metalloligands with Schiffꢀbase unit or
binaphthyl unit.7
Compared to singleꢀmetalꢀbased metalloligands, the clusterꢀbased metalloligands remain rarely
known in the formation of MOFs with promising catalytic properties. As a tetrahedral cluster with
accessible active metal centers, Cu4I4 binded with pyridine carboxylate ligand (L), is apt to form series
new metalloligands, featured [Cu4I4(L)4], whose carboxylic groups can unite other metal centers to
produce different inorganic building blocks. There is a useful strategy toward heterometallic MOFs to
use organic ligands with different functional groups and different donor atoms, like O and N atoms.8, 9
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Although a number of 3dꢀ4f compounds containing Cu+ ions, lanthanide ions (Ln3+) and pyridine
carboxylate ligands have been reported previously,8, 9 the combination of this [Cu4I4(L)4] metalloligands
with other transition metal ions to form new heterometallic 3dꢀ3d compounds is rarely explored.
Moreover, little experimental effort has focused on determining the heterometallic MOFs based on
tetrahedral Cu4I4 cluster for effectively heterogeneous catalysis.
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In this work, we report three threeꢀdimensional (3D) heterometallic clusterꢀorganic frameworks,
namely [(Cu4I4)3Zn8(ꢁ4ꢀO)(INA)12(H2O)4]ꢂ2(CH3COO)ꢂx(guest) (1; INA
=
isonicotinate);
and
[(Cu4I4)2Zn2(INA)4(DBO)6]ꢂx(guest) (2; DBO 1,4ꢀdiazabicyclo[2.2.2]octane)
=
[(Cu4I4)Mn2(INA)4(H2O)2DMF]ꢂx(guest) (3). All three compounds consist of metal carboxylate building
units linked by [Cu4I4(INA)4]4ꢀ or [Cu4I4(INA)2(DBO)2]2ꢀ metalloligands, but they exhibit distinct
structural topologies because of the different conformation of inorganic building blocks. The catalytic
activity of these compounds was evaluated by using the diethylzinc addition to aromatic aldehydes as a
test reaction. Factors that have been considered in this context include (1) the creation of open metal
sites on the framework, (2) reaction time, (3) reaction temperature, and (4) the incorporation of electronꢀ
withdrawing groups in aromatic aldehydes.
Experimental Section
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General Procedures.
All reagents were purchased commercially and used without further purification. All Powder Xꢀray
diffraction (PXRD) analyses were recorded on a Rigaku Dmax2500 diffractometer with Cu Kα radiation
(λ = 1.54056 Å) with a step size of 0.05°. Thermogravimetric studies were carried out on a NETSCHZ
STAꢀ449C thermoanalyzer with a heating rate of 10 °C/min under an air atmosphere. Gas adsorption
measurement was performed in the ASAP (Accelerated Surface Area and Porosimetry) 2020 System.
Fluorescence spectra were measured at room temperature with a HORIBA JobinꢀYvon FluoroMaxꢀ4
spectrometer. Conversion and yield values were determined by GC on a Supelco bꢀDex 120 column.
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Synthesis of [(Cu4I4)3Zn8(µ4-O)(INA)12(H2O)4]·2(CH3COO)·x(guest) (1). A 20 mL vial containing
CuI (0.095 g, 0.5 mmol), isonicotinic acid (0.062 g, 0.5 mmol), Zn(CH3COO)2ꢂ4H2O (0.080 g, 2 mmol),
5 drops triethylamine (TEA), 3 mL N,Nꢀdimethyl formamide (DMF) and 1.5 mL ethanol was sealed and
heated in an oven at 100 oC for 3 days. The vial was taken out and naturally cooled to room temperature.
After washed with fresh ethanol, yellow polyhedral crystals were obtained in pure phase (Yield: 150 mg,
75% based on CuI).
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Synthesis of [(Cu4I4)2Zn2(INA)4(DBO)6]·x(guest) (2). A 20 mL vial containing CuI (0.095 g, 0.5
mmol), isonicotinic acid (0.062, 0.5 mmol), Zn(NO3)2ꢂ6H2O (0.080 g, 2 mmol), 1,4ꢀ
diazabicyclo[2.2.2]octane (0.121 g, 1 mmol), 3 mL DMF and 1.5 mL ethanol was sealed and heated in
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an oven at 100 C for 3 days. The vial was taken out and naturally cooled to room temperature. After
washed with fresh ethanol, yellow block crystals were obtained in pure phase (Yield: 60 mg, 47% based
on CuI).
Synthesis of [(Cu4I4)Mn2(INA)4(H2O)2DMF]·x(guest) (3). A 20 mL vial containing CuI (0.095 g,
0.5 mmol), isonicotinic acid (0.062, 0.5 mmol), Mn(CH3COO)2ꢂ4H2O (0.080 g, 2 mmol), 3 mL DMF
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and 1.5 mL ethanol was sealed and heated in an oven at 100 C for 3 days. The vial was taken out and
naturally cooled to room temperature. After washed with fresh DMF, yellow clubꢀshaped crystals were
obtained in pure phase (Yield: 35 mg, 15% based on CuI).
Diethylzinc Additions to Aromatic Aldehydes with Solid Catalyst: Actived catalysts (20 mg) dried
under vacuum at 100 oC for 8 h was placed in a 25 mL Schlenk flask, and then vacuumized for 10 min.
3 mL of toluene was added via syringe under nitrogen. After the mixture was stirred for 30 min,
aromatic aldehydes (0.5 mmol) and diethylzinc (1 M in toluene, 1 mL, 1 mmol) were added. The
mixture was stirred under nitrogen at corresponding temperature and time, and then quenched with
saturated NH4Cl solution. The organic phase was separated and passed through a short silica gel column.
An aliquot was analyzed by GC to give the conversion and yield values.
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X-ray Crystallography: The diffraction data of 1-3 were collected on a Bruker Smart Apex CCD
diffractometer with graphite monochromated Mo Kα radiation (λ = 0.71073Å) at 293 K. Absorption
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corrections was applied by SADABS. The structure was solved by direct methods and refined with fullꢀ
matrix leastꢀsquares technique using SHELXTL. All nonꢀhydrogen atoms were refined with anisotropic
displacement parameters. The structures were solved by direct methods and refined on F2 fullꢀmatrix
leastꢀsquares using the SHELXTLꢀ97 program package. The total interstitial solvent molecule contents
were determined by thermogravimetric analysis (TGA). Crystal data for 1: cubic, a = b = c = 18.9120(3)
Å, V = 6764.14(19) Å3, T = 293(2) K, space group Pꢀ43n, Z = 2, 4145 reflections measured, 1416
independent reflections (Rint = 0.0355). The final R1 value was 0.0821 (I > 2σ(I)). The final wR(F2)
value was 0.2199 (I > 2σ(I)). Crystal data for 2: orthorhombic, a = 28.7510(8) Å, b = 18.0562(4) Å, c =
16.7272(5) Å, V = 8683.7(4) Å3, T = 293(2) K, space group Cmca, Z = 8, 7588 reflections measured,
3541 independent reflections (Rint = 0.0247). The final R1 value was 0.0468 (I > 2σ(I)). The final wR(F2)
value was 0.1439 (I > 2σ(I)). Crystal data for 3: monoclinic, a = 18.0043(8) Å, b = 21.1164(9) Å, c =
18.1594(14) Å, β = 93.344(5)°, V = 6892.2(7) Å3, T = 293(2) K, space group P2(1)/c, Z = 4, 16937
reflections measured, 8722 independent reflections (Rint = 0.0582). The final R1 value was 0.0577 (I >
2σ(I)). The final wR(F2) value was 0.1308 (I > 2σ(I)). The contribution of the disordered solvent
molecules in 1ꢀ3 was subtracted from the reflection data by the SQUEEZE method as implanted in
PLATON program. CCDCꢀ893051ꢀ893053 (1-3) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html.
Results and Discussion
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It is notable that the employment of mixed CuI and Zn2+ (or Mn2+) with INA ligand into such a
solvothermal assembly system is based on our careful consideration. The hard and soft coordination
mode of the INA ligand is widely known in many heterometallic 3dꢀ4f coordination polymers.8, 9 Here,
our interest is to apply this special coordination mode of the INA ligand to create a new clusterꢀbased
3dꢀ3d system. From these three structures, we achieved two aspects: 1) the both anticipated tetrahedral
[Cu4I4(INA)4]4ꢀ and [Cu4I4(INA)2(DBO)2]2ꢀ metalloligands can be in situ generated; 2) the second 3d
metal center (Zn2+or Mn2+) is participated into the assembly with carboxylate groups to form additional
metal carboxylate cluster including possible open metal sites.
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The structure of 1, where the tetrahedral [Cu4I4(INA)4]4ꢀ metalloligands link unusual Zn8(ꢁ4ꢀ
O)(COO)12(H2O)4 clusters into a (4,12)ꢀconnected network, is of particular interest. Following the hard
and soft (Lewis) acids and bases (HSAB) theory, the INA N atom binds to a tetrahedral Cu center and its
carboxylate O atoms coordinate to two Zn centers. The geometry of [Cu4I4(INA)4]4ꢀ metalloligand
generated in situ is just tetrahedral (Figure 1a).
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One prominent feature in the structure of 1 is the presence of another 12ꢀconnected tetrahedral Zn8(ꢁ4ꢀ
O)(COO)12(H2O)4 cluster. Such a cluster is truly unusual and can be considered as a tetrahedral ꢁ4ꢀO2ꢀ
center bringing four Zn2(COO)3 units together (Figure 1b). Compared to the famous Zn4(ꢁ4ꢀO) unit in
MOFꢀ5, this Zn8(ꢁ4ꢀO)(COO)12(H2O)4 cluster is a more super one with tetrahedral symmetry and higher
connectivity. It is interesting to note that each Zn center in this cluster also exhibits tetrahedral
coordination geometry with four oxygen atoms. Four vertical Zn centers of this cluster are all
coordinated by water molecules which are possibly removed to generate open metal sites for catalysis.
The resulting Cu4I4 cluster and Zn8(ꢁ4ꢀO)(COO)12(H2O)4 cluster are alternately linked each other
through the INA ligand into a 3D framework (Figure 1d). From the viewpoint of structural topology, the
whole framework of 1 can be topologically represented as a (4,12)ꢀconnected ith net with vertex symbol
of (430.630.86)(46)3 by reducing each Cu4I4 cluster as a 4ꢀconnected node and each Zn8(ꢁ4ꢀ
O)(COO)12(H2O)4 cluster as a 12ꢀconnected node (Figure 1e).10 Interestingly, the structural topology of
1 also can be considered from another point of view. If the ꢁ4ꢀO2ꢀ groups can be neglected in advance,
the nodes in 1 have changed to Cu4I4 and Zn2(COO)3(H2O) clusters (Figures 1a and 1c). Such assembly
between 3ꢀconnected Zn2(COO)3(H2O) node and 4ꢀconnected Cu4I4 node leads to a 3D openꢀframework
with (3,4)ꢀconnected ctn topology (Figures S1ꢀ2 in the supporting information). For such an empty
framework, structural interpenetration is difficult to avoid. Actually, a 4ꢀfold interpenetration of these
ctnꢀtype frameworks is found in the whole structure by using the TOPOS program (Figure 1f).
However, the assembly does not stop here and the next netꢀtoꢀnet assembly occurs. Through the ꢁ4ꢀO2ꢀ
centers, four interpenetrating ctnꢀtype frameworks are coordinatively linked into one single framework
with 4ꢀconnected selfꢀpenetrating topology (Figures 1d and 1f). Now each Zn2(COO)3 unit acts as a 4ꢀ
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connected node and the Cu4I4(INA)4 metalloligand keeps its 4ꢀconnectivity. The resulting 4ꢀconnected
net (denoted: tyx) derived from ctn subꢀnets has a vertex symbol (86) and exhibits interesting selfꢀ
penetrating feature (Figure 1f). To our knowledge, this new tyx topology has not been predicted before.
The observation of such unusual ctn net to tyx net assembly is mainly ascribed to presence of the ꢁ4ꢀO2ꢀ
group which creates a chance of interpenetration. Furthermore, the selfꢀpenetrating feature of the tyx net
is much easy to identify, because it is derived from the interpenetrating ctn nets.
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Despite the much high level of connectivity, the whole framework of 1 still has solventꢀaccessible
volume approximately 1755.9 Å3 per unit cell (6764.1 Å3), being equal to about 26.0% of the total
crystal volume estimated by PLATON program. The solvent guests in the free spaces were evidenced by
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TGA. The TGA curve of 1 showed the release of guest molecules between 25 and 250 C, leading to a
weight loss of 8.5% (Figure S3 in the supporting information). The phase purity of the bulk product of 1
was independently confirmed by powder Xꢀray diffraction (Figure S4 in the supporting information).
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Figure 1. a) The geometry of in situ generated [Cu4I4(INA)4]4ꢀ metalloligand in 1 (Cu: blue; I: violet; N:
sky blue; O: red; C: black); b) a 12ꢀconnected tetrahedral Zn8(ꢁ4ꢀO)(COO)12(H2O)4 cluster in 1(Zn:
green; O: red; C: black); c) the Zn2(COO)3(H2O) clusters (Zn: green; N: sky blue; O: red; C: black; H:
lime); d) a 3D framework resulted from the alternately linkage of Cu4I4 cluster and Zn8(ꢁ4ꢀ
O)(COO)12(H2O)4 cluster through the INA ligand in 1; e) a (4,12)ꢀconnected ith net by reducing each
Cu4I4 cluster as a 4ꢀconnected node and each Zn8(ꢁ4ꢀO)(COO)12(H2O)4 cluster as a 12ꢀconnected node; f)
the resulting 4ꢀconnected tyx net derived from ctn subꢀnets.
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When additional DBO was used in the reaction system of 1, another new compound 2 with distinct
structural feature was obtained. Our origin consideration on adding DBO for synthesis is to test the
template effect of DBO, but the coordination of DBO with metal centers results in the formation of a
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new compound 2. The structure of 2 also consists of similar Cu4I4 clusters, but each Cu4I4 unit is
surrounded by two INA and two DBO ligands, forming a new [Cu4I4(INA)2(DBO)2]2ꢀ metalloligand
(Figure 2a). Moreover, the metal carboxylate cluster in 2 is just a paddleꢀwheel Zn2(COO)4 unit with
two monodentately coordinate DBO ligands in two apical sites (Figure 2a). Each Cu4I4 cluster exhibits
as a tetrahedral 4ꢀconnected node to link two other Cu4I4 clusters through two DBO ligands and two
Zn2(COO)4 units through two INA ligands. The cooperative assembly between tetrahedral Cu4I4 cluster
and 4ꢀconnected planar Zn2(COO)4 unit leads to an open framework with large empty spaces (Figure
2a). Topological analysis indicates that one simple framework of 2 features an unusual binodal (4,4)ꢀ
connected bbf topology (Figure 2c).10 Furthermore, twoꢀfold interpenetration is occurred in the whole
framework, but the final framework still has solventꢀaccessible volume approximately 2494.7 Å3 per
unit cell (8683.7 Å3), being equal to about 28.7% of the total crystal volume estimated by PLATON
program (Figure 2d). The TGA curve of 2 shows only slight release of guest molecules between 25 and
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250 C, because the big terminal DBO ligands occlude the entrance to each cavity (Figure S5 in the
supporting information). The phase purity of the bulk product of 1 was independently confirmed by
powder Xꢀray diffraction (Figure S6 in the supporting information).
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Figure 2. a) The geometry of the [Cu4I4(INA)2(DBO)2]2ꢀ metalloligand and paddleꢀwheel Zn2(COO)4
unit in 2 (Cu: blue; I: violet; Zn: green; N: sky blue; O: red; C: black); b) a single framework with nanoꢀ
size 1D channels along c axis in 2; c) an unusual binodal (4,4)ꢀconnected bbf topology by reducing each
Cu4I4 cluster and paddleꢀwheel Zn2(COO)4 unit as a 4ꢀconnected node; d) the whole framework with
twoꢀfold interpenetration in 2.
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Compound 3 was solvothermally synthesized by mixing HINA, Mn(CH3COO)2ꢂ4H2O and CuI in
DMF/ethanol solution at 100 oC for three days. The structure of 3 also contains two kinds of clusters—
the familiar Cu4I4 and Mn2(COO)4(H2O)2(DMF) clusters. The in situ generated [Cu4I4(INA)4]4ꢀ
metalloligand in 3 is almost the same with that in 1. Two independent Mn centers in the
Mn2(COO)4(H2O)2(DMF) unit show octahderal coordination geometry. One Mn ion is fully coordinated
by the carboxylate oxygen atoms, while another one is only bonded by three carboxylate oxygen atoms
and has three additional coordination sites with two water molecules and one DMF molecule (Figure 3a).
If each carboxylate group is treated as one connecting point, each Mn2(COO)4(H2O)2(DMF) unit has a
pseudo tetrahedral geometry and is thus connected to four Cu4I4 clusters in a tetrahedral fashion. Further
tetrahedral assembly results in a diamondoid framework with large cages (Figures 3b and 3c). The edged
Cu4I4···Mn2 distances in each cage are in the range from 9.759 to 12.200 Å, and the maximum pore
dimension in each cage is about 15.0 Å. The resulting large cavities further induce twoꢀfold
interpenetration of the framework, whose interpenetration vector runs along the c axis (Figure 3d).
Despite twoꢀfold interpenetration, the structure generates 1D channel with a window size of 6×4.5 Å2
along the c axis. The free space in the structure of 3 without guest molecules is 50.4% as calculated by
PLATON program. These channels are occupied by the solvent molecules.
Both TGA and powder Xꢀray diffraction (PXRD) measurements were carried out to examine the
thermal behavior of 3 (Figures S7 and S8 in the supporting information). The TGA curve of 3 shows
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that the trapped and coordinated solvent molecules can be drastically removed before 310 C (weight
loss: 26.6%). After an obvious plateau between 310 and 350 °C, the framework decomposition started.
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However, such high porous material after dichloromethane exchange can hardly show any gas
adsorption (9.1 cm3/g for CO2 at 273 K and 1bar, 6.1 cm3/g for H2 and 4.8 cm3/g for N2 at 77 K and
1bar), because of the relaxation of the twoꢀfold interpenetrating framework attested by PXRD
measurements (Figure S8c and S9 in the supporting information).
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From the above structural description of three compounds, it is clear the formation of these clusterꢀ
based framework structures is influenced by multiple factors, such as the incorporation of auxiliary
ligands or the usage of different metal centers. The distinct structural topologies between 1 and 2 is
obviously associated with the incorporation of DBO ligand in the structure of 2. For 1 and 3, they have
the same [Cu4I4(INA)4]4ꢀ metalloligands but different secondary metal centers (Zn2+ in 1 and Mn2+ in 3),
so different frameworks are generated.
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Figure 3. a) The geometry of in situ generated [Cu4I4(INA)4]4ꢀ metalloligand and
Mn2(COO)4(H2O)2(DMF) unit in 3 (Cu: blue; I: violet; Mn: dark red; N: sky blue; O: red; C: black); b) a
single dia framework assembled by tetrahedral Cu4I4 cluster and 4ꢀconnected Mn2(COO)4(H2O)2(DMF)
unit; c) an binodal (4,4)ꢀconnected dia topology; d) twoꢀfold interpenetration is occurred in the whole
framework of 3 with large 1D channels along c axis.
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The photoluminescent properties of the asꢀsynthesized 1 and 2 were studied in the solid state with
excitation wavelength at 350 nm at room temperature (Figures S10 in the supporting information). 1 and
2 display emissions with maximum at 564 and 547 nm, respectively. Unlike other previously reported
Cu4I4L4 (L = ligand) cluster complexes with emission peaks occurring at ~590 nm,13 the emission peaks
observed in 1 and 2 all exhibit obvious blue shift, which attributed to the cooperative effect between
Cu4I4 unions and zincꢀbased clucters. As we known, no photoluminescent propertie of MOFs
constructed by Cu4I4 and zincꢀbased clucters has been reported before.
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To evaluate the catalytic activity of compounds 1ꢀ3 actived at 100 C under vacuum for 8 hours, we
used the diethylzinc addition to benzylaldehyde as a test reaction (Table 1 and Figure 4) and affirmed
the corresponding alcohol as the principal product. In a typical reaction, 20 mg (0.48 mmol %) sample
of 1 was used for the conversion of 0.5 mmol benzaldehyde in hexane at 0 oC. An excess of 100% ZnEt2
was employed with respect to the amount of benzaldehyde. The composition of the reaction mixture was
determined by gas chromatography (GC) (Figure S11 in the supporting information). After 8 h, the
reaction leaded to a 99.8% conversion of benzaldehyde, a 91.8% selectivity of product and a TOF of 6.5
hꢀ1. The same reaction conditions were used for testing the catalytic activity of compound 2 (20 mg, 0.73
mmol %) and 3 (20 mg, 1.53 mmol %). The results show that catalytic activity of 2 (Conv. of 99.8%,
selectivity of 94%, TOF of 8.5 hꢀ1) is similar to that of 1 but much higher than that of 3 (Conv. of
98.2%, selectivity of 79.0%, TOF of 2.7 hꢀ1). The lower selectivity in 3 maybe attribute to its unstable
porous framework. Moreover, the catalyst 1 and 2 show a higher activity and selectivity in the addition
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reaction of benzaldehyde than that obtained with other MOFs 8b,11
For example, the same raaction has
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also been catalyzed by a chiral MOF [Cd3Cl6L3]ꢂTi (L = (R)ꢀ6,6'ꢀdichloroꢀ2,2'ꢀdihydroxyꢀ1,1'ꢀ
binaphthylꢀ4,4'ꢀbipyridine) reported by Lin groups, giving high ee% of 83% and high yield of 99% but
low TOF of 1.3 hꢀ1 at room temperature; the cyanosilylation of benzaldehyde catalyzed by the MOF
{[Cd(L)2(DMF)2]ꢂ(ClO4)2ꢂ(2ꢂDMF)}n (L = bisꢀ(4ꢀimidazolꢀ1ꢀylꢀphenyl)ꢀdiazene) gave TOF of 4.3 hꢀ1 in
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14 h with 5 mol% catalyst loading at 0 C; the yields and TOFs of the cyanosilylation of benzaldehyde
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catalyzed the two activated Ln(btc) MOFs (btc = 1,3,5ꢀbenzenetricarboxylates; Ln = Er, Yb) reported by
Zou groups were always less than 61% and 3 hꢀ1, respectively. Thus, compound 1 was used for a more
comprehensive study because of its high yield and high catalytic activity. In addition to this remarkable
high catalytic activity, 1 has the advantage that Zn(II) and Cu(I) cannot be easily reduced by
benzaldehyde. Thus, the framework of 1 is intact after using as a catalyst, judging from the PXRD
pattern of the catalyst after diethylzinc addition (Figure S4 in the supporting information). Compared to
the PXRD pattern of the asꢀsynthesized sample, a slim redistribution of the peak intensities, but no
change of the peak positionswas observed.
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Table 1. Highly efficient and selective diethylzinc addition to aromatic aldehydes catalyzed by MOF
solids a
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stirred. Reaction temperature, C. Reaction time, hour. Conversion % and selectivity % were
determined by GC. e The second cycle. f The third cycle. g TOF = turn over frequency (moles of reactants
reacted per moles of active sides unit time), hꢀ1. Note: the standard deviations are based on three
repeated experiments
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Figure 4. Time selectivity plot for the diethylzinc addition reactions of benzaldehyde catalyzed by
catalysts 1, 2 and 3 at 0 oC.
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To prove the heterogeneous mechanism of the diethylzinc addition to aromatic aldehydes, leaching
test of 1 by removing the solid catalyst after 1 h and continuing reaction for another 8 h were performed.
No further conversion was noted, proving heterogeneity of the catalyst (Figure S12 in the supporting
information).
A recycling test with three consecutive runs was performed to check if the catalyst 1 could be reused.
For all three reactions, the conversion after 8 hours was always great (99%). A selectivity of 92.2% was
achieved in the first run after 8 hours. However, the selectivity in the following two runs decreased to
88.0% and 80.1%, respectively. The results show that catalyst 1 can be reused several times with a
somewhat reduced activity.
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The catalytic activity of 1 at different reaction temperatures (0, 20 and 40 C) were also checked
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(Figures S13 and S14 in the supporting information). For the reaction at 20 C, 99.8% conversion of
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temperature increased to 40 C, one hour was enough to get a complete conversion, but the selectivity
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further decreased to 54.7%. It is clear that reaction temperature strongly affects the reaction rate and
selectivity. At lower temperature, the catalyst benefits from a longer lifetime to avoid deactivation
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processes while the reaction rate also decreases, may attributing to slower removal of products from
active metallic sides.
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Aiming to determine the potential applicability of the protocol, the substrate scope of the diethylzinc
addition reaction was then investigated with the use of three different aromatic aldehydes, 4ꢀtrifluoroꢀpꢀ
tolualdehyde, 4ꢀchlorobenzaldehyde and 4ꢀmethoxybenzaldehyde. The results are summarized in Table
1, and Figure 5. As shown in Table 1, entries 8ꢀ10, 99.8% conversion of 4ꢀtrifluoroꢀpꢀtolualdehyde was
obtained within 3 h to give the corresponding alcohol in 92.0% selectivity. Compared with 4ꢀtrifluoroꢀpꢀ
tolualdehyde, 4ꢀchlorobenzaldehyde gave a similiar conversion within 4 h but a lower selectivity of
75.8%. However, the addition reaction of 4ꢀmethoxybenzaldehyde with diethylzinc afforded the
incomplete conversion of 85.1% and low selectivity of 74.2% within 8 h. The results indicate a strong
correlation between the electronic properties of substituents and the reaction rates.12 Thus, electron
withdrawing substituted groups on the armoatic aldehyde, such as ꢀCF3 and ꢀCl, favor the addition
reactionwhile electron donating group, such as ꢀOMe, disfavor the reaction.
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Figure 5. Time selectivity plot for the diethylzinc addition reactions of benzaldehyde catalyzed by
catalysts 1, 2 and 3 at 0 oC.
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In summary, through the cooperative assembly of tetrahedral Cu4I4 and metalꢀcarboxylate clusters,
three 3dꢀ3d heterometallic MOFs with potential catalytic meter centers and interesting structural
topologies have successfully synthesized and structurally characterized. All three clusterꢀorganic
frameworks have notable catalytic activity on the diethylzinc addition to aromatic aldehydes, and the
catalytic properties of compound 1 with unusual clusterꢀbased (4,12)ꢀconnected structure have been
studied in detail. The results reveal that the heterogeneous catalysis of the diethylzinc addition to
aromatic aldehydes by using MOF as catalyst is determined by several experimental factors, such as
temperature, reaction time and the incorporation of electronꢀwithdrawing groups in aromatic aldehydes.
It also demonstrates that clusterꢀbased MOFs are potential catalysts for future applications.
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Acknowledgment. We thank the support of this work by National Basic Research Program of China
(973 Programs 2011CB932504 and 2012CB821705), NSFC (21073191, 21221001), NSF of Fujian
Province (2011J06005) and CAS (XDA07070200). We also thank Prof. Ling Song for her valuable
discussion.
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Supporting Information Available: additional Figures, TGA, powder Xꢀray diffraction patterns,
sorption isotherms and CIF files. This material is available free of charge via the Internet at
http://pubs.acs.org.
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REFERENCES.
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(1) (a) Férey, G. Chem. Soc. Rev. 2008, 37, 191. (b) Cui, Y. J.; Yue, Y. F.; Qian, G. D.; Chen, B. L.
Chem. Rev. 2012, 112, 1126. (c) Yoon, M.; Srirambalaji, R.; Kim, K. Chem. Rev. 2012, 112, 1196.
(d) Liu, Y.; Boey, F.; Lao, L. L.; Zhang, H.; Liu, X.; Zhang, Q. Chem Asian J. 2011, 6, 1004. (e)
Lee, J.Y.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp, J. T. Chem. Soc. Rev.,
2009, 38, 1450. (f) Horcajada, P.; Gref, R.; Baati, T.; Allan, P. K.; Maurin, G.; Couvreur, P.; Férey,
G.; Morris, R. E.; Serre, C. Chem. Rev. 2012, 112, 1232.
49
329
330
331
50
51
52
53
54
55
56
57332
58
59
60
333
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338
339
340
341
342
343
(2) (a) D’Alessandro, D. M.; Smit, B.; Long, J. R. Angew. Chem. Int. Ed. 2010, 49, 6058. (b) Lin, X.;
1
2
3
4
5
6
7
8
Jia, J.; Zhao, X.; Thomas, K. M.; Blake, A. J.; Walker, G. S.; Champness, N. R.; Hubberstey, P.;
Schröder, M. Angew. Chem. Int. Ed. 2006, 45, 7358. (c) Guo, Z.
Zhou, Y. Xiang, S. Chen, Z. Yang, Y. Zhou, W. O’Keeffe, M.
;
Wu, H.
;
Gadipelli, S.
;
Liao, T.
;
;
;
;
;
;
;
Chen B. Angew. Chem. Int. Ed.
,
9
2011, 50, 3178. (d) Chen, B.; Xiang, S.; Qian, G. Acc. Chem. Res, 2010, 43, 1115. (e) Jiang, H. L.;
Tatsu, Y.; Lu, Z. H.; Xu, Q. J. Am. Chem. Soc. 2010, 132, 5586. (f) Li, G.; Yu, W.; Cui, Y. J. Am.
Chem. Soc. 2008, 130, 4582. (g) Liu, Y.; Xuan, W.; Cui, Y. Adv. Mater. 2010, 22, 4112. (h) Zhu, C.;
Yuan, G.; Chen, X.; Yang, Z.; Cui, Y. J. Am. Chem. Soc. 2012, 134, 8058.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
(3) (a) Lin, Q.; Wu, T.; Zheng, S.; Bu, X.; Feng, P. Chem. Commun. 2011, 47, 11852. (b) Jiang, G.; Wu,
T.; Zheng, SꢀT; Zhao, X.; Lin, Q.; Bu, X.; Feng, P. Crystal Growth & Design 2011, 11, 3713. (c)
Zheng, S.; Bu, J. J.; Wu, T.; Chou, C.; Feng, P.; Bu, X. Angew. Chem. Int. Ed. 2011, 50, 8858. (d)
Chen, L.; Bu, X. Chem. Mater. 2006, 18, 1857. (e) An, J.; Rosi, N. L. J. Am. Chem. Soc. 2010, 132,
5578. (f) Zheng, S.ꢀT.; Zhang, J.; Yang, G.ꢀY. Angew. Chem. Int. Ed. 2008, 47, 3909.
(4) (a) Li, J.ꢀR.; Kuppler, R. J.; Zhou, H.ꢀC. Chem. Soc.Rev. 2009, 38, 1477. (b) Zeng, M.ꢀH.; Wang, Q.ꢀ
X.; Tan, Y.ꢀX.; Hu, S.; Zhao, H.ꢀX.; Long, L.ꢀS. J. Am. Chem. Soc. 2010, 132, 2561. (c) Zheng, S.;
Wu, T.; Zuo, F.; Chou, CꢀT.; Feng, P.; Bu, X. J. Am. Chem. Soc. 2012, 134, 1934. (d) Wang, F.;
Liu, Z.ꢀS.; Yang, H.; Tan, Y.ꢀX.; Zhang, J. Angew. Chem. Int. Ed. 2011, 50, 450.
24344
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51
52
53
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55
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57
58
59
60
(5) (a) Wu, C.ꢀD.; Lin, W. Angew. Chem. Int. Ed. 2005, 44, 1958. (b) Ranocchiari, M.; Bokhoven, J. A.
Phys. Chem. Chem. Phys. 2011, 13, 6388. (c) Nickerl, G.; Henschel, A.; Grünker, R.; Gedrich, K.;
Kaskel, S. Chem. Ing. Tech., 2011, 83, 90. (d) Ma, L.; Wu, C.ꢀD.; Wanderley, M. M.; Lin, W.
Angew. Chem. Int. Ed. 2010, 49, 8244.
(6) (a) Wang, Z.; Chen, G.; Ding, K. Chem. Rev. 2009, 109, 322. (b) Henschel, A.; Gedrich, K.;
Kraehnert, R.; Kaskel, S. Chem. Commun. 2008, 4192. (c) Schlichte, K.; Kratzke, T.; Kaskel, S.
Microporous Mesoporous Mater. 2004, 73, 81.
(7) Llabrés i Xamena, F. X.; Casanova, O.; Galiasso Tailleur, R.; Garcia, H.; Corma, A. J. Catal. 2008,
255, 220.
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369
(8) (a) Sakata, Y.; Hiraoka, S.; Shionoya, M. Chem. Eur. J. 2010, 16, 3318. (b) Nayak, S.; Harms, K.;
Dehnen, S. Inorg. Chem. 2011, 50, 2714. (c) Gu, X.; Xue, D. Cryst. Growth Des. 2007, 9, 1726. (d)
Zhang, M.ꢀB.; Zhang, J.; Zheng, S.ꢀT.; Yang, G.ꢀY. Angew. Chem. Int. Ed. 2005, 44, 1385. (e)
Cheng, J.ꢀW.; Zhang, J.; Zheng, S.ꢀT.; Zhang, M.ꢀB.; Yang, G.ꢀY. Angew. Chem., Int. Ed. 2006, 45,
73. (f) Gu, X.; Xue, D. Inorg. Chem. 2007, 46, 5349.
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(9) (a) Zeng, R.ꢀH.; Peng, G.; Qiu, Y.ꢀC.; Zheng, S.ꢀR.; Li, W.ꢀS.; Zhang, W.ꢀX.; Deng, H.; Cai, Y.ꢀP.
CrystEngComm 2011, 13, 3910. (b) Cheng, J.ꢀW.; Zhang, J.; Zheng, S.ꢀT.; Yang, G.ꢀY. Chem. Eur.
J. 2008, 14, 88.
(10)
(a) Blatov, V. A.; Carlucci, L.; Ciani, G.; Proserpio, D. M. CrystEngComm 2004, 6, 377; (b)
Alexandrov, E. V.; Blatov, V. A.; Kochetkov, A. V.; Proserpio, D. M. CrystEngComm 2011, 12,
24370
25
3947.
26
27
371
(11) (a) Gustafsson, M.; Bartoszewicz, A.; MartínꢀMatute, B.; Sun, J.; Grins, J.; Zhao, T.; Li, Z.; Zhu
28
29
30
31
32
33
34
35
36
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40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
372
373
374
375
376
377
378
379
380
381
382
383
384
G.; Zou, X. Chem. Mater. 2010, 22, 3316. (b) Fuijta, M.; Kwon, Y. J.; Washizu, S.; Ogura, K. J.
Am. Chem. Soc. 1994, 116, 1151. (c) Horike, S.; Dincǎ, M.; Tamaki, K.; Long, J. R. J. Am. Chem.
Soc. 2008, 130, 5854. (d) Wu, C.ꢀD.; Hu, A.; Zhang, L.; Lin, W. J. Am. Chem. Soc. 2005, 127, 8940.
(e) Wu, C.ꢀD.; Lin, W. Angew. Chem. Int. Ed. 2007, 46, 1075. f) Sharma, M. K.; Singh, P. P.;
Bharadwaj, P, K. J. Mol. Catal. AꢀChem. 2011, 342, 6.
(12) Zhou, X.; Wu, X.; Yang, B.; Xiao, J. J. Mol. Catal. A: Chem. 2012, 357, 133.
(13) (a) Braga, D.; Maini, L.; Mazzeo, P. P.; Ventura, B. Chem. Eur. J. 2010, 16, 1553. (b) Bi, M.; Li,
G.; Zou, Y.; Shi, Z.; Feng, S. Inorg. Chem. 2007, 46, 607. (c) Bi, M.; Li, G.; Hua, J.; Liu, X.; Hu, Y.;
Shi, Z.; Feng, S. CrystEngComm 2007, 9, 984. (d) Zhang, Y.; Wu, T.; Dou, T.; Liu, R.; Bu, X.; Feng,
P. Crystal Growth & Design 2010, 10, 2047. (e) Zhang, Y.; He, X.; Zhang, J.; Feng, P. Crystal
Growth & Design 2011, 11, 29.
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The cooperative assembly of tetrahedral Cu4I4 and metalꢀcarboxylate clusters with potential open metal
sites leads to three 3dꢀ3d heterometallic MOFs with interesting structural topologies and catalytic
properties.
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