Two scandium coordination polymers: Rapid synthesis and catalytic properties

Article abstract of DOI:10.1039/c9ce00969h

Two scandium coordination polymers (Sc-CPs), [Sc(L¹)₂(DMF)] (DMF = N,N′-dimethyl formamide, H₂L¹ = pyrazine-2,3-dicarboxylic acid) (1) and [Sc(L²)(C₂O₄)_0.5(H₂

Full text of DOI:10.1039/c9ce00969h

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Two scandium coordination polymers: rapid synthesis and
catalytic property
Ziqian Zhu,a Yufang Tao,a Yansong Jiang,a Liying Zhang,b Jianing Xu,a Li Wang*a and Yong Fan*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Two scandium coordination polymers (Sc-CPs), [Sc(L1)2(DMF)] (DMF = N,N’- dimethyl formamide, H2L1 = pyrazine-2,3-
dicarboxylic acid) (1) and [Sc(L2)(C2O4)0.5(H2O)2]·H2O (H2L2 = pyrazine-2,5-dicarboxylic acid) (2) were prepared via
hydrothermal and microwave heating (MV) techniques. It is noted that MV can effectively accelerate the reaction
compared with conventional hydrothermal method and decrease the crystal size of the samples. 1 shows a 1D no-planar
double chain, while 2 exhibits a brick-like 2D network. After activation, 1 and 2 exhibit good catalytic performance for
cyanosilylation reaction of aromatic aldehydes, in addition, the catalysts prepared by MV method perform better catalytic
activity compared with those synthesized by conventional hydrothermal method.
www.rsc.org/
crystal nucleation, and low yield from batch to batch,
which greatly limits the development of Sc-CP catalysts.11-
Recently, microwave heating technique (MV) has been
1. Introduction
16
Coordination polymers (CPs) as heterogeneous catalysts
have attracted great attention, owing to their advantages
in catalytic reactions, including high catalyst loading, more
accessible and identifiable catalytic centers, and the
tunable design of the framework structure.1 Additionally,
from environmental and economic viewpoints, these
heterogeneous catalysts are desired to improve the
processes with high conversion and product purity, easy
separation, efficient recycling.2 Among them, scandium-
based CPs (Sc-CPs) are of great interest and have been
successfully used as Lewis acid catalysts in many
successfully applied to prepare functional CPs.17
Compared with conventional heating methods, MV is a
simple, cost-effective, and efficient heating method which
allows short reaction time, fast kinetics of crystal
nucleation and growth, and high yields of desirable
products with few or no secondary products.18-19
Therefore, MV heating is a promising method for the
syntheses of new Sc-CP catalysts.
On the other hand, the choice of organic moieties is
very important for the construction Sc-CPs20 and minor
change of organic ligands can lead to remarkably different
architectures21-25 and functions.26-28 Due to Sc3+ ions
prefer to bind to hard donor atoms,29-32 the utilization of
N-heterocyclic carboxylic acid ligand not only can direct
the dimensionality and topology of the targeted
frameworks, but also can incorporate functional sites into
Sc-CPs which can be active for catalysis as intrinsic sites.33-
reactions.3-7
For
example,
the
first
Sc-CP
[Sc2(OOCC2H4COO)2.5(OH)] shows Lewis acidity of the
Friedel-Crafts acylation reaction with 30% yield after 24
hours.3 [Sc2(C4O4)3] can be used as a heterogeneous
catalyst in cyanosilylation (90% yield, reacting 12 hours).4
MIL-100(Sc) performs activity in a series of reactions, such
as imine formation, Michael reaction, indole reaction and
carbonylene reaction.5-7
34
Therefore, to explore new functional Sc-CPs, we select
pyrazine-2,3-dicarboxylic acid (H2L1)35-43 and pyrazine-2,5-
dicarboxylic acid (H2L2)44-46 as structural builders based on
the following factors: (1) the carboxylate oxygen atoms
preferentially bond to Sc3+ ions over two nitrogen atoms
of pyrazine which can provide free Lewis basic sites;47-48 (2)
they are sterically rigid and chemically robust, leading to
frameworks of high thermal and chemical stability.30,32,49
To our knowledge, Sc-CPs are commonly synthesized
by hydrothermal
/ solvent-thermal reactions with
conventional heating methods.8-10 However, this method
usually leads to high synthesis temperature, long time of
a..College of Chemistry, Jilin University, Changchun 130012, Jilin, P. R. China.
Email: lwang99@jlu.edu.cn, mrfy@jlu.edu.cn
In this work, two new Sc-CPs [Sc(L1)2(DMF)] (
[Sc(L2)(C2O4)0.5(H2O)2]·H2O
via conventional
1) and
b.College of Food Engineering, Jilin Engineering Normal University, Changchun
130052, P. R. China
(2)
hydrothermal heating and MV heating have been
successfully prepared and structurally characterized.
Electronic Supplementary Information (ESI) available: Crystal data and structure
refinement, XRD, TGA, IR and a plausible mechanism for the cyanosilylation
reaction. CCDC reference number: 1054439 for
crystallographic data in CIF or other
DOI: 10.1039/x0xx00000x
1
, 1054440 for
electronic
2
. For ESI and
format see
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J. Name., 2013, 00, 1-3 | 1
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It is noted that the MV method effectively shortened
the reaction time and decreased the size of the samples.
shows a 1D no-planar double chain, while exhibits a
3552 (s), 3108 (s), 1648 (s), 1480 (m), 1391V(isew),A1rt3ic1le6On(lsin)e,
1181 (s), 1048 (s), 955 (w), 852 (m).DOI: 10.1039/C9CE00969H
1
2
brick-like 2D network. After activation, they both exhibit
good catalytic performance for cyanosilylation reaction of
aromatic aldehydes. Herein, the synthetic condition,
2.3 MV synthesis of 1 and 2
[Sc(L1)2(DMF)] (1m, m = microwave): Sc(NO3)3·6H2O
(0.0845 g, 0.25 mmol), H2L1 (0.084 g, 0.5 mmol), DMF
(8.75 mL) and H2O (1.25 mL) were mixed in a 60 mL Teflon
reactor. The mixture was stirred for 30 min, and then
closed in microwave digestion meter, keeping the
pressure at 0.2 Mpa for 6 min by MV (P = 400 W). The
system was allowed to cool to room temperature. White
powders were obtained with the yield of 86.91%. Anal.
Calc. for 1m: C, 38.62; H, 3.93; N, 15.01. Found: C, 38.21;
H, 3.99; N, 16.17. IR data (KBr pellet cm-1): 3428 (m), 3116
(w), 2924 (w), 1652 (s), 1374 (s), 1115 (s), 901 (m), 848 (s).
crystal morphology and catalytic property of
1 and 2
obtained through two methods independently are
discussed in detail.
2. Experimental
2.1 Materials and Physical Measurements
All the reagents of analytical grade were obtained from
commercial sources and used without further purification.
MV was performed on a MDS-6 microwave digestion
meter. Size and morphology of the produced structures
were determined by a scanning electron microscope
(SEM, SU8020, Hitachi, Japan) and a transmission electron
microscope (TEM, JEM-2200FS, JEOL, Japan). Powder X-
[Sc(L2)(C2O4)0.5(H2O)2] ·H2O (2m,
m = microwave):
ScCl3·6H2O (0.259 g, 1 mmol), H2L2 (0.204 g, 1 mmol),
HNO3 (2 mL, 1 M) and H2O (10 mL) were mixed in a 60 mL
Teflon reactor. The mixture was stirred for 30 min, and
then closed in microwave digestion meter, keeping the
pressure at 0.1 Mpa for 3 min by MV (P = 400 W). Light
yellow powders were obtained with the yield of 83.15%.
Anal. Calc. for 2m: C, 27.17; H, 2.59; N, 9.05. Found: C,
26.42; H, 2.95; N, 8.79. IR data (KBr pellet cm-1): 3552 (s),
3108 (s), 1648 (s), 1480 (m), 1391 (s), 1316 (s), 1181 (s),
1048 (s), 955 (w), 852 (m).
ray diffraction (PXRD) data were collected on
a
SHIMADAZU XRD-6000 diffractometer with Cu-Kα
radiation (λ = 1.5418 Å). The elemental analyses (C, H and
N) were performed on an Elemental Vario EL cube CHNOS
Elemental Analyzer. The infrared (IR) spectra were
recorded over 400−4000 cm−1 region on a Nicolet Impact
410 FTIR spectrometer using KBr pellets. The thermal
gravimetric analyses (TGA) were performed on a Perkin-
Elmer TGA 7 thermogravimetric analyzer instrument in
atmospheric environment with a heating rate of 10 °C
2.4 X-ray structure determinations
Suitable single crystals of
crystal X-ray diffraction analyses. Crystal data for
1
-2
were selected for single-
were
1-2
1
min-1. The H-NMR spectra were recorded on Bruker 400
collected on a Rigaku RAXIS-RAPID diffractometer using
Mo Kα radiation (λ = 0.71073 Å). Crystallographic
structures were solved by direct methods and refined by
full-matrix least-squares on F2 using SHELXTL-2014
software package. All the metal atoms were located first,
and then O, N, and C atoms of the compounds were
subsequently found in difference Fourier maps. H atoms
of the ligands were placed geometrically, and H atoms of
the water molecules could not be located but were
included in the formula. All non-hydrogen atoms were
MHz spectrometer, with chemical shifts (δ) being given in
ppm. The percent conversion was determined by NMR.
2.2 Hydrothermal synthesis of 1 and 2
[Sc(L1)2(DMF)] (1h, h = hydrothermal): Sc(NO3)3·6H2O
(0.0169 g, 0.05 mmol), H2L1 (0.0168 g, 0.1 mmol), DMF
(1.75 mL) and H2O (0.25 mL) were placed in a 20 mL glass
bottle which was then sealed and heated at 80 °C for 24 h.
The system was allowed to cool to room temperature
naturally. Colourless crystals were obtained with the yield
of 42.53% based on scandium. Anal. Calc. for 1h: C, 38.62;
H, 3.93; N, 15.01. Found: C, 38.21; H, 3.99; N, 16.17. IR
data (KBr pellet cm-1): 3428 (m), 3116 (w), 2924 (w), 1652
(s), 1374 (s), 1115 (s), 901 (m), 848 (s).
refined anisotropically. The unit cell volume of
2 included
a region of disordered solvent which could not be
modelled as discrete atomic sites. We employed
PLATON/SQUEEZE to calculate the contribution to the
diffraction from the solvent region. The final formula was
calculated from the SQUEEZE results combined with
elemental analysis data and TGA data and was derived
from crystallographic data combined with elemental and
thermogravimetric analysis data. Crystallographic data for
[Sc(L2)(C2O4)0.5(H2O)2] ·H2O (2h,
h = hydrothermal):
ScCl3·6H2O (0.0259 g, 0.1 mmol), H2L2 (0.0204 g, 0.1
mmol), HNO3 (200 μL, 1 M) and H2O (1 mL) were
immersed in a 23 mL Teflon reactor which was then
sealed and heated at 150 °C for 24 h. The system was
allowed to cool to room temperature. Light yellow
crystals were obtained with the yield of 53.15% based on
scandium. Anal. Calc. for 2h: C, 27.17; H, 2.59; N, 9.05.
Found: C, 26.42; H, 2.95; N, 8.79. IR data (KBr pellet cm-1):
1-2 (CCDC 1054439-1054440) had been deposited with
Cambridge Crystallographic Data Centre. Data could be
obtained free of charge upon request at
www.ccdc.cam.ac.uk/data_request/cif. [Or from the
Cambridge Crystallographic Data Centre, 12 Union Road,
2 | J. Name., 2012, 00, 1-3
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S1, S2). As shown in Fig. 1, the size of 1m wasV1iewμmArticle Online
× 6 μm
Cambridge CB2 1EZ, UK; Fax: (internet.) +44 1223/336
033; E-mail: deposit@ccdc.cam.ac.uk]. The detailed
crystallographic data and structure refinement
m
and the size of 1h was 0.3 mm
×
2 mDmOI.: 1T0h.1e03s9iz/eC9oCfE2009w69aHs
4.5 mm.
200 nm
×
600 nm and the size of 2h was 1.5 mm
×
parameters for
selected bond lengths and angles data were presented in
Table S2.
1
-
2
were summarized in Table S1, and
The sizes of 1m and 2m were obviously smaller than those
of 1h and 2h. The crystals of 1h and 2h were macroscopic,
while the crystals of 1m and 2m were too small to be seen
clearly by the naked eyes.
2.5 Activation experiments
Samples of
heated at 110 °C for 12 h under vacuum before the
catalytic reaction. Samples of were activated at 330 °C
1 were soaked in CH3OH for 24 h and then
2
for 4 h before the catalytic reaction. Each activated
sample was retained in a plastic sample tube and sealed
for preservation.
Fig. 1 The morphology of 1m, 1h, 2m, 2h. (1h, 2h: The fluorescence
microscope images illuminated with UV light)
2.6 Catalytic experiments
For the experiments of cyanosilylation catalysis, activated
catalyst (0.05 mmol), (CH3)3SiCN (1.2 mmol), p-
nitrobenzaldehyde (0.5 mmol) in CH3CN (5 mL) were
sequentially added to a standard 20 mL vial. The reaction
mixtures were stirred at room temperature. The reactions
were monitored by 1HNMR spectroscopy and the
conversion yield was determined to the sum of integrals
of all signals (aldehyde and product).
Fig. 2 (a)-(b) SEM of 1m; (c)-(d) TEM of 2m.
The Scanning Electron Microscope (SEM) images (Fig.
2a, b) showed 1m prepared by MV method was micro-size.
The Transmission Electron Microscope (TEM) images (Fig.
2c, d) showed 2m prepared by MV method was nano-size.
2.7 Recycling catalysis experiments
For the recyclability tests, the reactions were performed
under the same conditions as described above, except for
using the recycled catalyst. After the catalytic reaction,
the catalyst was separated from the reaction mixture by
filtration, during which washed with 10 mL CH3OH for 5
times, then dried at 80 °C for 12 h.
3.2 Description of crystal structure
Crystal Structure of [Sc(L1)2(DMF)] (1). Single-crystal X-
ray diffraction analysis revealed that
1 represented a 1D
chain and crystallized in the triclinic space group P-1.
There were two Sc3+ ions, two DMF molecules and four L1
ligands in the asymmetric unit (As shown in Fig. 3b). Sc3+
ion was seven-coordinated and described as a distorted
pentagonal bipyramidal geometry, in which four
coordinated oxygen atoms were from the carboxylic
groups of four different L1 ligands, the remaining oxygen
atom was from the DMF molecular, and two nitrogen
atoms were from the pyrazine rings of two different L1
ligands (Fig. 3a). The Sc-O bond lengths varied from
2.033(3) to 2.163(3) Å and the Sc-N bond lengths varied
from 2.422(3) to 2.497(4) Å. The bond angles of O-Sc-O
3. Results and discussion
3.1 Synthesis and morphology (1h, 2h, h = hydrothermal; 1m,
2m, m = microwave)
Table 1 Synthesis comparison of 1 and 2.
ranged from 76.20(11) to 179.56(13)
°, while the bond
angles of O-Sc-N ranged from 67.23(12) to 151.24(12)
°
.
All of the bond lengths and angles were comparable to
those reported in other scandium compounds.50 All
carboxyl groups of the L1 ligand were completely
deprotonated, in agreement with the IR spectra (Fig. S3),
in which no strong absorption peaks in range of 1690-
1730 cm-1 were observed.51
As shown in Table 1, MV took much shorter time than
hydrothermal heating. The yields of 1m and 2m were
86.91% and 83.15%, respectively, which were higher than
those of 1h and 2h. The XRD patterns demonstrated that
the single crystal structure of 1m and 1h were the same,
the crystal structure of 2m and 2h were also the same (Fig.
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Each L1 ligand exhibited same coordination mode as
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DOI: 10.1039/C9CE00969H
shown in figure 3c, which acted as a μ2-bridge to link two
Sc3+ ions. Two scandium centers and two L1 ligands
formed a grid, in which pyrazine rings of the L1 ligand
were parallel each other. The composition and
conformation of the grids enabled them to extend along
[010] direction by sharing the scandium ions, resulting in a
1D no-planar double chain. As shown in figure 3d, the
adjacent chains were arranged in ABAB stacking sequence
and there was no super molecular interaction between
the adjacent chains, and the inter-chain interaction forces
were uniquely the van der Waals interactions.
Fig. 4 (a) Coordination environment of Sc3+ ions in 2 (Symmetry codes: a –x+2,
b
c
-y, -z+1, –x+1, -y, -z+1, –x+1,-y,-z); (b) Coordination modes of ligands in 2;
(c) Coordination of L2 with the scandium centers generated the 1D chain and
the 1D chains generated the 2D layer by bridging the C2O4 ions; (d) The Sc3+
2-
ion was simplified as a 3-connected node, the L2 ligand and C2O4 ion were
2-
considered as linear linkers; (e) 2D network in 2 and topological network. All
the hydrogen atoms were omitted for the sake of clarity.
In
2
, L2 ligands adopted bis-N,O chelating fashion to
2-
link two scandium centers and C2O4 ion showed
bidentate bridging coordination mode as presented in
Figure 4b. The L2 ligand connected the Sc3+ ions to form a
bent chain with the adjacent Sc-Sc distance of 7.707 Å.
Fig.
3 (a) Schematic representation of distorted ScO5N2 coordination
polyhedron in 1; (b) Grid constructed from two Sc3+ ions and two bridging L1
ligands; (c) Coordination mode of L1 ligand with Sc3+ ions; (d) Packing
diagrams of [Sc(L1)2(DMF)] chains. All the hydrogen atoms were omitted for
clarity
2-
Then adjacent chains were interlinked by C2O4 ions to
Crystal Structure of [Sc(L2)(C2O4)0.5(H2O)2]·H2O (2).
give
a
brick-like 2D network (Fig. 4c). To better
, the topological analysis
understand the structure of
2
Single-crystal X-ray diffraction analysis revealed that
2
approach was employed. The net contained two kinds of
nodes: the Sc3+ ion could be considered as a 3-connected
node, while L2 ligand and C2O4 ion were considered as
linear linkers, respectively. Thus the 2D network of
could be described as a 3-connected topological network
(Fig. 4e).
crystallized in triclinic space group P-1. There were one
unique Sc3+ ion, two half L2 ligands, one half oxalic acid,
two coordinated water molecules and one free molecule
of water in the asymmetric unit. As shown in Fig. 4a, Sc3+
ion was eight-coordinated by two oxygen atoms and two
nitrogen atoms from two independent L2 ligands, two
oxygen atoms from one oxalic acid molecule, and two
oxygen atoms from two coordinated water molecules. It
formed a dodecahedron motif, which displayed high
coordinating ability of Sc3+ ions. The bond lengths of Sc-O
varied from 2.1402(16) to 2.2767(16) Å while the Sc-N
bond lengths varied from 2.4463(19) to 2.480(2) Å. The
2-
2
3.3 Characterization
The phase purities of 1m 1h 2m and 2h were confirmed by
, ,
XRD measurements and each XRD pattern of the as-
synthesized sample was consistent with the simulated one
(Fig. S1, S2). The differences in intensity might be owing to
the preferred orientation of the powder samples.
bond angles of O-Sc-O ranged from 71.94(6) to 144.99(6)
°
and the O-Sc-N ranged from 68.40(6) to 145.16(7) . All of
°
The solvent and thermal stability of CPs were
expected to play the critical role in their performance as
the bond lengths and angles were comparable to those
reported in other scandium compounds.50 All carboxyl
groups of the L2 ligand were completely deprotonated, in
agreement with the IR spectra (Fig. S4), in which no strong
absorption peaks in range of 1690-1730cm-1 were
observed.51
heterogeneous Lewis catalysts. Herein,
1 and 2 were
immersed in different pure organic solvents for 24 h and
the PXRD patterns of treated samples were collected (Fig.
5a, 5b). The results showed that the crystal structures of
1
and still remained unchanged. Notably, kept stable in
2
2
4 | J. Name., 2012, 00, 1-3
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conversion of 99%, 2m catalyzed the reactionViienw2Arhticlwe Oitnhlinae
DOI: 10.1039/C9CE00969H
conversion of 99% (Table 2). The results suggested that
the Sc-CPs acted as good catalysts for cyanosilylation
under room temperature, especially Sc-CPs obtained from
MV methods exhibited better catalytic property. Blank
reactions were performed by carrying out the
cyanosilylation of p-nitrobenzaldehyde without catalyst at
the same condition (NPT and air environment). The test
reaction showed that it could hardly react without
catalyst (Entry 5, Table 2).
Table 2 Results for the heterogeneous cyanosilylation of carbonyl substrates in
the presence of 1h, 1m, 2h and 2m.
e
O
OSiM
3
.
ca
t
H
CN
e
M
3SiCN
CH3CN
O2N
O2N
Time
Conversion
yield (%)
Entry
Cat.
(h)
20
7.5
8
1
2
3
4
5
1h
1m
99
99
99
99
0
2h
2m
2
Fig. 5 (a) PXRD patterns of 1 in different solvents; (b) PXRD patterns of 2 in
different solvents.
Blank
No reaction
boiling water for 24 h. Therefore, unlike most Lewis acids
which were decomposed or deactivated in the present of
water, our new heterogeneous Lewis catalysts were
stable both in water and organic solvents (Fig. 5).
Reactions conditions: room temperature under air; (CH3)3SiCN, 1.2 mmol; p-
nitrobenzaldehyde, 0.5 mmol; catalysts: 0.05 mmol (10 mol %); Cat.
represented for 1h, 1m, 2h and 2m, which were activated. The conversion yield
was determined by 1H-NMR.
As 2m showed better catalytic ability than 1m, we
1
released all of the water molecules (obs. 5.52%;
further studied the substrate generality of 2m
. As
calc. 6.44%) in the temperature range of 25-110 °C.
Further heating led to 27.96% weight loss in the
temperature range of 110-275 °C which might be ascribed
to the removal of DMF molecules (calc. 26.12%). The
weight loss (obs. 41.40%; calc. 42.78%) from 275 to 681 °C
summarized in table 3, strong electron-acceptor
substrates (p-nitrobenzaldehyde, p-cyanobenzaldehyde,
p-trifluoromethylbenzaldehyde) reached 99% conversion
yield within 2 hours under activated 2m catalyst. Weak
electron-acceptor substrates (p-fluorobenzaldehyde, p-
chlorobenzaldehyde, p-bromobenzaldehyde) reached 99%
conversion yield within 6 hours under activated 2m
was attributed to the collapse of the framework of
1 (Fig.
S5). lost all of its lattice water and coordinated water
2
molecules (obs. 13.40%; calc. 16.82%) in the temperature
range of 98-140 °C. The weight loss of 60.58% between
141 °C and 616 °C was assigned to the collapse of network
(calc. 58.87%) (Fig. S6).
catalyst.
Strong
electron-donor
substrate
(p-
methoxybenzaldehyde) reached 61.3% conversion yield
within 22 hours under activated 2m catalyst. Weak
electron-donor
reached 99% conversion yield within 4.5 hours under
activated 2m catalyst. When the large substrates,
substrate
(p-methylbenzaldehyde)
3.4 Catalytic Studies
The catalytic properties of
1-2 were investigated as
valeraldehyde,
cinnamaldehyde
and
p-
heterogeneous Lewis acid catalysts for the cyanosilylation
of p-nitrobenzaldehyde (Table 2). Aldehydic substrates
and trimethylsilyl cyanide (1:2 molar ratio) were running
for the catalytic reaction at room temperature.
Conversions of the reactions were determined by 1H-NMR
spectroscopy. For hydrothermal synthetic compounds: 1h
catalyzed the reaction in 20 h with a conversion of 99%, 2h
reached a 99% conversion rate within 8 h. For MV
compounds: 1m catalyzed the reaction in 7.5 h with a
phenoxybenzaldehyde were utilized, 99% products yields
were observed after 10, 48 and 48 hours, respectively. For
small substrates, such as pyridine-4-carboxaldehyde and
thiophene-2-carbaldehyde, the conversion yield was 99%
after 30 minutes and 10 hours for each. When 1-
naphthaldehyde was tested, 99% conversion yield was
shown after 41 hours.
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Table 3 Different aldehydic substrates for cyanosilylation catalyzed by 2m.
O
e
3
iM
OS
.
ca
t
H
N
C
R
e
3S C
M
i N
R
25 ℃ CH3CN
25 ℃ No solvent
Entry
Substrate
Conversion
yield (%)
Conversion
yield (%)
Time (h)
Time (h)
H
O
C
C
C
1
2
2
99
99
99
99
99
99
61.3
99
99
99
99
99
99
0.5
99
99
99
99
99
99
99
99
99
99
99
99
99
N
O2
H
O
0.5
1
0.25
1
N
C
H
O
3
F
3C
F
H
C
O
4
4
1.5
1.5
1.5
12
4
H
C
O
5
6
l
C
H
C
O
6
4
r
B
H
C
O
7
22
4.5
10
48
0.5
48
10
H
3CO
H
C
O
8
H
3C
H
C
O
9
6
10
11
12
13
10
0.5
41
5
H
C
O
H
C O
N
O
S
H
O
C
H
C
O
H
C
O
14
41
99
19
99
H
C
O
15
24
50
-
-
N
O2
Reactions conditions: room temperature under air; (CH3)3SiCN, 1.2 mmol; p-nitrobenzaldehyde, 0.5 mmol; catalysts: 0.05 mmol (10 mol %), cat. represented for
2m (activation: Entry 1-14), 2@m (non-activation: Entry 15); the conversion yield was determined by 1H-NMR.
6 | J. Name., 2012, 00, 1-3
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We also investigated the catalytic performance of 2m
To investigate whether an excess of homogeneous
catalyst from 2m had some influence on the catalytic
activity, we separated the organic matter by filtration
after 22 hours. Then the filtrate was stirred for further 26
hours. As presented in Fig. 6, no conversion of products is
observed. The result demonstrated that the catalysis was
actually heterogeneous. The lowest molar ratio of 2m and
aldehydic substrate was 5 mol%. Because the small rigid
ligands exhibited less modes of coordination, they could
link the metal sites intensively and increase the density of
the metal (scandium) sites in a unit volume. 2m could be
easily recovered by filtration and reused at least in 4
cycles without obvious loss of conversion (Fig. S7). The
XRD patterns of recycled 2m after 4 cycles revealed that
the structure remained unchanged. (Fig. S2)
under solvent-free condition. The results indicated that
the catalytic capacities of 2m toward isonicotinaldehyde
had equal efficiencies both under CH3CN solvent and
solvent-free conditions. Expect isonicotinaldehyde, other
substrates exhibited better performance under solvent-
free condition by 2m. Notably, the fastest reaction was p-
cyanobenzaldehyde with 99% conversion yield in 15
minutes. (Table 3)
For the comparison of activation and non-activation
sample, the non-activation catalyst of 2@m also had been
tested in the cyanosilylation (Entry 15, Table 3). After
activation, 2m exhibited much better catalytic
performance. We found that 2m presents 99% convention
yield after 2 hours, while 2@m reached 50% conversion
yield in 24 hours. So, the activation was an essential
procedure to prepare the catalyst, which could give more
open metal sites.
4. Conclusions
In summary, two new Sc-CPs
1 and 2 were synthetized
under hydrothermal conditions and microwave heating.
They both exhibited high thermal and solvents stabilities
and could be used as Lewis acid catalysts for the
cyanosilylation of aldehyde. Notably, the products
prepared by MV exhibited much smaller size, higher
yields, better catalytic activity compared with those
synthesized by hydrothermal heating. Further work will be
focus on the synthesis of nano CPs with Lewis acid sites by
MV method along with their catalytic properties.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors gratefully acknowledge the financial support
through the National Natural Science Foundation of China
Fig. 6 Conversion of the 4-Phenoxybenzaldehyde to
4-Phenoxybenzylidenemalononitrile, by 2m under CH3CN (black) and
filtrated after 22 h of traction (red).
(Grant
Nos.
21171065,
21201077,
21401005)
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DOI: 10.1039/C9CE00969H
Graphical abstract
Two Scandium coordination polymers: rapid synthesis and
catalytic property
Ziqian Zhu, a Yufang Tao, a Yansong Jiang,a Liying Zhang, b Jianing Xu, a Li Wang
*a and Yong Fan *a
a College of Chemistry, Jilin University, Changchun 130012, P. R. China
b College of Food Engineering Normal University, Changchun 130052, P. R. China
 Two new scandium coordination polymers were synthesized under MV and
hydrothermal methods, which exhibit good catalytic performance.