Ce(III)-Based frameworks: From 1d chain to 3d porous metal-organic framework

Article abstract of DOI:10.1021/acs.cgd.9b00949

The reaction of pyridine-2,4-dicarboxylic acid (2,4-H₂ pydc) with Ce(NO₃)₃6H₂O, by applying only minor changes to the reaction conditions, generated a series of new one-, two-, and three-dimensional (1D, 2D, and 3D) coordination polymers, namely, [Ce(pydc)(Hpydc)(H₂O)₄]_n (1), [Ce(pydc)(Hpydc)(H₂O)₂]_n (2), and {[Ce₃(pydc)₄(H₂O)₂NO₃]4H₂O}_n (3). The ancillary ligand interaction as well as the reaction conditions determine the specific coordination modes for the Hpydc^- and pydc^2- ligands and, in turn, discriminate between 1D, 2D, and 3D frameworks. Characterization of the prepared materials was performed using single-crystal and powder X-ray diffraction analysis, Fourier transform infrared spectroscopy, CHN elemental analysis, thermogravimetric analysis, and nitrogen adsorption/desorption techniques. Compound 1 consists of 1D chains, that compose of Ce³⁺ ions bridged by Hpydc^- and pydc^2- ligands, which further link via noncovalent interactions to form a 3D supramolecular architecture. Compound 2 assembles into 2D sheets with 1D channels. Similarly, via hydrogen-bonding interactions between two adjacent sheets, the 2D layers are further stacked into the final 3D supramolecular structure. Compound 3 is a 3D metal-organic framework (MOF), showing 1D helical channels. The progressive skeletal variation from the 1D chains (1) to 2D sheets (2) and 3D framework (3) is attributed to the flexibility of both the Ce(III) coordination sphere and coordination modes of the Hpydc^- and pydc^2- ligands under different reaction conditions. The three compounds illustrate how the tuning of the coordination geometry of Ce(III) translates into different dimensionality, which is readily influenced by reaction temperature and ancillary ligand presence. Moreover, the porosity of MOF 3 was confirmed by N₂ and CO₂ gas adsorption/desorption. Finally, the catalytic activity of MOF 3 was examined in acetalization reactions in a series of aromatic aldehydes with methanol.

Full text of DOI:10.1021/acs.cgd.9b00949

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Article
Ce(III)-based Frameworks: From 1D Chain
to 3D Porous Metal-Organic Framework
Parviz Gohari Derakhshandeh, Sara Abednatanzi, Karen Leus, Jan
Janczak, Rik Van Deun, Pascal Van Der Voort, and Kristof Van Hecke
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b00949 • Publication Date (Web): 24 Oct 2019
Downloaded from pubs.acs.org on October 27, 2019
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Ce(III)-based Frameworks: From 1D Chain to 3D Porous Metal-Organic
Framework
*a,b†
a†
a
c
Parviz Gohari Derakhshandeh
, Sara Abednatanzi , Karen Leus , Jan Janczak , Rik Van
d
a
*b
Deun , Pascal Van Der Voort , Kristof Van Hecke
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a
COMOC, Department of Chemistry, Center for Ordered Materials, Organometallics and
Catalysis, Ghent University, Krijgslaan 281 – Building S3, B-9000 Ghent, Belgium
b
XStruct, Department of Chemistry, Ghent University, Krijgslaan 281 – Building S3, B-9000
Ghent, Belgium
c
Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box
1
410, 50-950 Wroclaw, Poland
d
L3 – Luminescent Lanthanide Lab, Department of Chemistry, Ghent University, Krijgslaan 281
– Building S3, B-9000 Ghent, Belgium
†
Both authors contributed equally to this work
ABSTRACT
The reaction of pyridine-2,4-dicarboxylic acid (H pydc) with Ce(NO ) .6H O, by applying only
2
3 3
2
minor changes to the reaction conditions, generated a series of new one-, two-, and three-
dimensional coordination polymers namely, [Ce(pydc)(Hpydc)(H O) ] (1),
[Ce(pydc)(Hpydc)(H O) ] (2), and {[Ce (pydc) (H O) NO ].4H O} (3). The ancillary ligand
2
4 n
2
2 n
3
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3
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n
interaction as well as the reaction conditions determine the specific coordination modes for the
-
2-
Hpydc and pydc ligands and, in turn, discriminate between 1D, 2D, and 3D frameworks.
Characterization of the prepared materials was performed using single-crystal and powder X-ray
diffraction analysis, Fourier transform infrared, CHN elemental analysis, thermogravimetric
analysis and nitrogen adsorption/desorption techniques. Compound 1 consists of 1D chains, that
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compose of Ce ions bridged by Hpydc and pydc ligands, which further link via non-covalent
interactions to form a 3D supramolecular architecture. Compound 2 assembles into 2D sheets with
1D channels. Similarly, via hydrogen bonding interactions between two adjacent sheets, the 2D
layers are further stacked into the final 3D supramolecular structure. Compound 3 is a 3D metal-
organic framework (MOF), showing 1D helical channels. The progressive skeletal variation from
the 1D chains (1) to 2D sheets (2) and 3D framework (3) is attributed to the flexibility of both the
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Ce(III) coordination sphere and coordination modes of the Hpydc and pydc ligands under
different reaction conditions. The three compounds illustrate how the tuning of the coordination
geometry of Ce(III) translates into different dimensionality, which is readily influenced by reaction
temperature and ancillary ligand presence. Moreover, the porosity of MOF 3 was confirmed by
N and CO gas adsorption/desorption. Finally, the catalytic activity of MOF 3 was examined in
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acetalization reactions in a series of aromatic aldehydes with methanol.
INTRODUCTION
Metal-organic frameworks (MOFs) are a class of porous materials constructed from inorganic
metal nodes, connected via/through multidentate organic bridging ligands. These nanoporous
solids have received tremendous attention because of their large specific surface area and
especially their structural variety, making them outstanding candidates to be used for various
applications such as catalysis , gas storage , magnetism , sensing and drug delivery11.
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Within this context, the design of coordination polymers (CPs) and MOFs have gained widespread
interest during the last decades due to the vast diversity of organic ligands and metal nodes that
can be incorporated in such compounds to construct intriguing architectures and topologies.
Numerous attempts have been geared for the design of CPs and MOFs, using the local geometry
of metal ions and functional ligands. Nevertheless, it is still challenging to control the
dimensionality of the target compounds, structural topology and pore dimensions to obtain
advanced MOF materials, suitable for more specialized applications12-15
.
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Lanthanide (Ln) CPs have attracted current research efforts due to their high and significant
flexibility in coordination modes and numbers, as they can incorporate various modular and
adjustable multi-dimensional framework materials16-22. The combination of lanthanide
luminescence, magnetic, and Lewis acid properties, with the diversity and features of CPs, can
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potentially be applied in heterogeneous catalysis23-25, luminescent molecular thermometers26-28
,
sensors29-32, and magnetic compounds . The coordination modes in transition metals are mostly
controlled by d-orbital directional features. In contrast, due to the shielded valence orbitals in
lanthanide ions, they do not display specific coordination geometries and show significant
flexibility in both coordination numbers and geometries. Therefore, design and control over the
coordination sphere of lanthanide frameworks appears to be challenging, due to the effect of
several factors, such as metal-ligand interactions, auxiliary ligand nature, outer-sphere counter ion,
hydrogen bonding groups and reaction conditions (temperature, solvent, pH, etc.). So far, very few
studies have reported the rational design and synthesis of rare earth CPs and MOFs. The report of
Ayhan et al. described the structural coordination chemistry of two new Ce(III)-based MOFs. In
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this case, small changes to the reaction conditions resulted in distinctive structures . Another study
demonstrated the formation of tubular Ln-based formworks depending on the reaction conditions
-
-
as well as the counterion. In the presence of Cl or NO anions, a tubular structure was formed,
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-
-
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while by using BF and OAc anions, a zigzag 2D compound was obtained .
4
Since Ln coordination compounds display significant flexibility in both coordination numbers and
geometries, we targeted Ce(III)-based frameworks as promising candidates for designing new
structures36-37. The large ionic radius of Ce(III) ions allows to adjust coordination modes by
adapting reaction conditions to produce distinctive structures. In this work, we report the design
and synthesis of three new Ce(III)-based frameworks using 2,4-pyridinedicarboxylic acid as a
linker. Small changes to the reaction conditions led to three different structures ranging from a
one-dimensional coordination polymer to a three-dimensional porous MOF. Moreover, the
catalytic properties of 3D MOF in acetalization reactions of different aldehydes with methanol
were investigated.
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EXPERIMENTAL SECTION
Materials and General Methods. All chemicals were purchased from commercial sources and
used without further purification. Chemical bonding was analyzed by infrared spectroscopy,
using a Thermo Scientific FT-IR spectrometer (type Nicolet 6700) equipped with a DRIFTS-cell.
Samples were prepared by mixing the powders with KBr. The samples were measured in the
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50-4000 cm range. Thermogravimetric analysis (TGA) and Differential Thermal Analysis
DTA) were performed with a Shimadzu TGA-51 and a DTA-50 apparatus under flowing air at
(
-1
-1
5
0 mL min and a heating rate of 10 ºC min . Nitrogen sorption studies were performed at -196
°C using a Belsorp-mini II gas analyzer. Before the adsorption experiments, the sample was
degassed under vacuum at 120 °C for 24 h. XRD patterns were recorded on a Thermo Scientific
ARLX’TRA diffractometer equipped with a Cu Kα (λ = 1.5405 Å) source, a goniometer and a
Peltier cooled Si (Li) solid state detector. In order to determine the conversion of the products, an
ultra-fast GC equipped with a flame ionization detector (FID) and a 5% diphenyl/95%
polydimethylsiloxane column with 10 m length and 0.10 mm internal diameter was applied.
-1
Helium was used as the carrier gas and the flow rate was programmed to be 0.8 mL min . The
reaction products were recognized using a TRACE GC × GC (Thermo, Interscience) coupled to
a TEMPUS TOFMS detector (Thermo, Interscience). The first column consists of a dimethyl
polysiloxane
package and has a length of 50 m with an internal diameter of 0.25 mm, whereas the second
column has a length of 2 m with an internal diameter of 0.15 mm. The package of the latter is
5
0% phenyl polysilphenylene-siloxane.
X-ray Crystallography. For the structures of 1 and 2, X-ray intensity data were collected at 100
K, on a Rigaku Oxford Diffraction Supernova Dual Source (Cu at zero) diffractometer equipped
with an Atlas CCD detector using  scans and CuK ( = 1.54184 Å) or MoK ( = 0.71073 Å)
radiation, for 1 and 2, respectively. For the structure of 3, graphite monochromatic Mo-K
radiation (λ = 0.71073 Å) on a four-circle  geometry KUMA KM-4 diffractometer, with a two-
dimensional area CCD detector, was used. The images were interpreted and integrated with the
3
8
39
program CrysAlisPro . Using Olex2 , the structures were solved by direct methods using the
2
SHELXT program and refined by full-matrix least-squares on F using the SHELXL program
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package40-41. Non-hydrogen atoms were anisotropically refined and the hydrogen atoms in the
riding mode and isotropic temperature factors fixed at 1.2 times U(eq) of the parent atoms.
Hydroxyl H-atoms were located when possible through a Fourier difference electron density map
(refined with isotropic temperature factors fixed at 1.5 times U(eq)). In crystal 3 it was possible
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to localize and refine some of the disordered solvent/water molecules. The rest of the solvent
molecules (nicotinamide) are highly disordered. The correct modelling of the disordered
molecules was not possible and we performed a “squeeze” treatment to remove the scattering
contribution of these molecules, which could not to be satisfactory modelled. In total, 61
electrons were removed from solvent accessible voids in a P1 unit cell. As one nicotinamide
molecule equals 64 electrons, it’s most likely that one nicotinamide molecule is disordered, or
th
(
as Z = 4), there’s an extra of 1/4 of a nicotinamide molecule per formula unit
C H Ce N O ).
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The final difference Fourier maps showed no peaks of chemical significance. CCDC 1897917-
897919 contain the supplementary crystallographic data for this paper and can be obtained free
1
of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44-1223-
3
36033; or deposit@ccdc.cam.ac.uk).
Synthesis. [Ce(pydc)(Hpydc)(H O) ] (1). A mixture of Ce(NO ) ·6H O (0.218 g, 0.5 mmol) and
2
4 n
3 3
2
2,4-H pydc (0.126 g, 0.75 mmol) was refluxed for 1 h in 5 mL of water. The resulting solution
2
was filtered and left to stand at room temperature. Pale-yellow single crystals, suitable for X-ray
crystallography, were obtained by slow evaporation after five weeks (yield 63%). Elemental Anal.
Calcd for C H CeN O : C, 30.94; H, 2.78; N, 5.15%. Found: C, 31.51; H, 3.34; N, 4.87%. IR
1
4
15
2
12
-1
(cm ): 3249 br/m, 1677 w, 1587 s, 1548 m, 1479 w, 1440 w, 1392 m, 1371 s, 1280 m, 1093 w,
012 w, 777 m.
1
[
Ce(pydc)(Hpydc)(H O) ] (2). A mixture of Ce(NO ) ·6H O (0.218 g, 0.5 mmol) and 2,4-H pydc
2 2 n 3 3 2 2
(0.126 g, 0.75 mmol) in 3 mL of H O was placed in a 12 mL Teflon-lined stainless steel autoclave.
2
The mixture was heated to 100 °C within 15 min, then kept at this temperature for 1 h and cooled
to ambient temperature within 24 h. Light-yellow crystals of 2 were filtered off, washed with water
and dried in air (yield 60%). Elemental Anal. Calcd for C H CeN O : C, 33.11; H, 2.18; N,
1
4
11
2
10
-1
5.51%. Found: C, 32.89; H, 2.16; N, 5.11%. IR (cm ): 3326 br/m, 3120 br, 1693 m, 1666 w, 1604
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s, 1562 m, 1471 m, 1427 m, 1371 m, 1276 m, 1249m, 1191 w, 1093 w, 1006 w, 939 w, 875 w,
771 s, 707 s.
{
[Ce (pydc) (H O) NO ].4H O 0.25C H N O} (3). A mixture of Ce(NO ) ·6H O (0.218 g, 0.5
3 4 2 2 3 2 6 6 2 n 3 3 2
mmol), 2,4-H pydc (0.126 g, 0.75 mmol) and nicotinamide (0.062 g, 0.5 mmol) in 3 mL of H O
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was placed in a 12 mL Teflon-lined stainless steel autoclave. The mixture was heated to 100 °C
within 15 min, then kept at this temperature for 1 h and cooled to ambient temperature within 24
h. Yellow crystals of 3 were filtered off, washed with water and dried in air (yield 51%). Elemental
Anal. Calcd for C29.5H25.5Ce N O25.25: C, 27.60; H, 2.00; N, 6.00%. Found: C, 30.31; H, 2.30; N,
3
5.5
th
5.35% (an extra of 1/4 of a nicotinamide molecule was taken into account in the elemental
-1
analysis, according to the X-ray analysis) IR (cm ): 3305 br/m, 1645 s, 1592 vs, 1481 s, 1454 s,
402 vs, 1305 w, 1245 w, 1095 w, 1014 m, 883 w, 831 w, 788s, 725s.
1
In addition, compound 3 can also be obtained by performing the reaction at 150 °C instead of 100
C and without the addition of nicotinamide, however in this case the crystals were not suitable
°
for the X-ray single crystal analysis.
General procedure for the acetalization reaction of benzaldehyde. During a typical catalytic
test, MOF 3 (0.008mmol, 10 mg), dodecane as an internal standard (0.2 mmol), benzaldehyde
(0.33 mmol) and methanol (0.5 ml) were added into a Schlenk tube. The tube was sealed and then
heated to 40 °C for 24 h. After each catalytic run, the catalyst was recovered by filtration, washed
with methanol and used directly in the subsequent runs. Samples were withdrawn after 24 h
reaction, and after cooling and dilution with the solvent, were analyzed using an ultra-fast gas
chromatograph (Thermo, Interscience) equipped with a flame ionization detector (FID).
RESULTS AND DISCUSSION
Synthesis and Preliminary Characterization. CP 1, [Ce(pydc)(Hpydc)(H O) ] , was
2
4 n
synthesized by conventional heating of Ce(NO ) ·6H O and 2,4-H pydc in a molar ratio of 2:3 in
3 3
2
2
water at 100 °C. After slow evaporation within 5 weeks, pale-yellow single crystals of 1 were
obtained. In addition, a yellow precipitation of 1 can be obtained in a shorter time by refluxing a
more concentrated solution for 3 h in water. CP 2, [Ce(pydc)(Hpydc)(H O) ] , was synthesized
2
2 n
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with the same reaction mixture as 1 but using a hydrothermal condition at 100 °C. After cooling
of the mixture during 24 h to room temperature, light-yellow crystals of 2 were prepared. MOF 3,
{
[Ce (pydc) (H O) NO ].4H O} , was synthesized under the same conditions as 2. However,
3 4 2 2 3 2 n
nicotinamide was added as an ancillary ligand, which gives the yellow suitable for the X-ray
analysis single crystals of 3. Although the nicotinamide ligand is not coordinated in the product,
its presence is crucial for the growth of the crystalline 3D MOF 3, since without it the 2D CP 2 is
obtained. The presence of trace amounts of disordered nicotinamide in 3 was confirmed during the
refinement of the crystal structure, as well as by observing some discrepancy between calculated
and experimental results of elemental analysis. All of the prepared compounds are stable in air.
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The IR spectra of all compounds show characteristic strong and broad bands for the coordinated
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-1
carboxylate groups (COO ) of the 2,4-pydc ligands in the ranges of 1587-1604 cm and 1371-
-1
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402 cm , for the asymmetric and symmetric stretching vibrations, respectively. In addition, the
characteristic broad peaks of the O-H vibration of water and/or carboxylic acid groups centered at
-1
-1
-1
around 3241 cm (1), 3318 (2) cm and 3305 cm (3) (Figure S1).
The thermal stability of 1, 2 and 3 was determined by means of thermogravimetric analysis (TGA).
The CP 1 is stable up to 148 °C and then starts to completely decompose till 722 °C with a mass
loss of 63.18% (calc. 67.7%). The exothermic peak at 473-548 °C in the DTA curve shows that
compound 1 is fully decomposed. CP 2 reveals three mass loss steps after 172.6 °C. The
coordination framework is thermally stable up to 397 °C and at higher temperature, with an
exothermic peak at 397-522 °C, the decomposition appears with a mass loss of 63.3% (calc.
6
6.0%). The TGA profile for MOF 3 shows a first weight loss step of 11.8% up to 148.8 °C, which
is probably attributed to the loss of four water molecules and a nitrate anion (calc. 10.7%). The
second mass loss of 2.8% occurs at 224 °C which may be due to the loss of two coordinated water
molecules (calc. 2.9%). On further heating, the decomposition of the organic components in 3 are
observed, showing an exothermic peak at 393-498 °C (Figure S2).
The experimental powder XRD patterns for compounds 1, 2 and 3 are in good agreement with the
corresponding simulated ones (Figure S3).
Structural Analysis. The reactions of the 2,4-H pydc ligand with Ce(NO ) .6H O led to the
2
3 3
2
formation of three 1D, 2D and 3D coordination frameworks. The structures of these compounds
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3
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7
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9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
were characterized by single-crystal X-ray diffraction. The crystallographic data and structure
refinement parameters for all materials are summarized in Table 1. The corresponding bond
lengths and angles in the coordination sphere of the Ce(III) cations are listed in Table S1. The
coordination modes of the pydc ligand in compounds 1, 2 and 3 are presented in scheme 1.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Table 1. Crystal data and refinement details for 1, 2 and 3
Empirical formula
Formula weight
Temperature
C
14
H
15CeN
2
O12 (1)
C
14
H
11CeN
2
O10 (2)
28 3 5
C H24Ce N O25 (3)
543.40
100.0 K
1.5418 Å
triclinic
P-1
507.37
100.0 K
0.71073 Å
triclinic
P-1
1250.88
100.0 K
Wavelength
0.71073 Å
tetragonal
Crystal system
Space group
3 1
P4 2 2
Unit cell dimensions
a = 6.3729(4) Å
b = 6.6115(2) Å
c = 19.9859(6) Å
α = 82.857(3)°
β = 81.281(4)°
γ = 81.673(4)°
819.06(6) Å3
2
a = 6.2373(2) Å
b = 9.3746(5) Å
c = 14.2072(5) Å
α = 72.685(4)°
β = 84.587(3)°
γ =71.604(4)°
752.55(6) Å3
2
a = 9.6303(6) Å
b = 9.6303(6) Å
c = 52.293(3) Å
α = 90°
β = 90°
γ = 90°
Volume
4849.8(7) Å3
4
Z
Density (calculated)
Absorption coefficient
F(000)
2.203 Mg/m3
22.211 mm-1
2.239 Mg/m3
3.091 mm-1
1.697 Mg/m3
2.894 mm-1
534.0
494.0
2356
0.18 x 0.07 x 0.068 mm3
0.294 x 0.147 x 0.089 mm3
0.17 x 0.18 x 0.19 mm3
Crystal size
Theta range for data
collection
9.00 to 150.706°
4.77 to 59.36°
2.4 to 29.5°
Index ranges
-7 h 7
-8 k 7
-8 h 8
-12 h 13
-12 k 12
-69 l 66
-12 k 12
-18 l 19
-22 l 25
Reflections collected
Independent reflections
Absorption correction
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R. [I>2sigma(I)]
R indices (all data)
10829
16655
52792
3285 [R(int) = 0.0632]
Numerical
3837 [R(int) = 0.0818]
Numerical
6251 [R(int) = 0.050]
Numerical
Full-matrix least-squares on F2
3285 / 13 / 289
1.042
Full-matrix least-squares on F2
3837 / 6 / 257
1.044
Full-matrix least-squares on F2
6251 / 0 / 272
1.006
R
R
-
1
1
= 0.0422, wR
= 0.0445, wR
2
2
= 0.1088
= 0.1114
R
R
-
1
= 0.0383, wR
= 0.0509, wR
2
= 0.0681
= 0.0735
R
R
1
= 0.0478, wR
= 0.0520, wR
2
= 0.1142
= 0.1164
1
2
1
2
Flack parameter
-0.014(15)
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Largest diff. peak, hole
1.41 and -1.35 e.Å-3
1.08 and -1.19 e.Å-3
1.75 and -1.57 e.Å-3
Crystal structure of 1. CP 1 crystallizes in the triclinic centrosymmetric space group P-1. The
2
-
-
asymmetric unit of 1 contains one Ce(III) cation coordinated by one pydc and one Hpydc anionic
ligands and four coordinated water molecules. The central Ce(III) ion is nine-coordinated to eight
oxygen atoms, from four water molecules, four carboxylate groups, and one nitrogen atom of a
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
-
2-
pydc ligand (Figure 1a). In 1, two Ce(III) centers are connected via two pydc ligands to produce
a binuclear unit. These units are connected to each other by carboxylic groups to make a one-
2
-
dimensional channel (Figure 1b and 1c). In fact, each pydc ligand acts as a tetradentate bridging
ligand and is coordinated to one Ce(III) in a bidentate fashion through the pyridine nitrogen atom
and a carboxylate oxygen atom and two more Ce(III) ions in a monodentate fashion through single
-
carboxylate oxygen atoms. Furthermore, a Hpydc ligand is bound to each Ce(III) center through
a single carboxylate oxygen atom. As shown in scheme 1a and 1b, in compound 1 two different
coordination modes of pydc are observed, which are coordinated to 1 and 3 distinct Ce(III) ions,
respectively. Extensive non-covalent interactions such as π···π stacking interactions and strong
O−H···O hydrogen bonds exist between two neighboring chains. The π···π stacking interactions
(with centroid-centroid distances of 3.712 Å) between single 1D chains, as illustrated in Figure 1d,
plays an important role in the final framework. Furthermore, the coordinated water molecules
contribute to the formation of intermolecular hydrogen bonds involving carboxylate O atoms
(Table S2). As a result, the 1D chains are further assembled into a 3D supramolecular network
4
2
(Figure 1d and 1e). To describe the 1D architecture of 1 more clearly, the TOPOS program was
used to analyze the topological structure. If every Ce ion is regarded as a node and each Hpydc-
2
-
and pydc ligands serves as a linker, CP 1 could simplify as a 3-c net (uninodal net) topological
2
structure, characterized by {4 .6} point symbol (Figure 4a).
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1
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1
1
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2
2
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2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
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5
5
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0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 1. (a) Coordination environment of the Ce(III) cation in 1. (b, c) Fragment of the 1D coordination polymer
chain of 1. (d, e) Fragment of the 3D supramolecular framework of 1.
Scheme 1. The coordination modes of the 2,4-pydc ligands in the (a, b) structure 1, (c,d) structure 2 and (e,f)
structure 3.
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Crystal structure of 2. CP 2 crystallizes in the triclinic centrosymmetric space group P-1 and the
2
-
-
asymmetric unit consists of a Ce(III) cation, one pydc and one Hpydc ligands and two
coordinated water molecules. Here, the Hpydc- ligand has a protonated carboxyl group instead of
2
-
a protonated pyridine nitrogen atom. The Ce(III) center is coordinated to five pydc units and two
water molecules to form an overall nine-coordinated local geometry of the metal center (Figure
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
-
2a). Three pydc units are monodentately coordinated to the Ce(III) center through a single
2
-
carboxylate atom and two remaining pydc units are coordinated in a bidentate fashion, similar to
the one seen in CP 1, through a carboxylate oxygen atom and a pyridine nitrogen atom. As
2
-
indicated in scheme 1c and 1d in compound 2 also two different coordination modes of pydc are
observed, which are coordinated to 2 and 3 distinct Ce(III) ions, respectively. Finally, two water
molecules are bound to complete the nine-coordination of the Ce(III). Viewing down the a-axis
reveals that the Ce(III) metal ions are linked via a carboxylate group, from one of the pydc2-
linkages. Furthermore, another carboxylate group is bridging the Ce(III) ions to complete the
overall 2D structure (Figure 2b-2d). Similar to the CP 1, extensive face-to-face π···π stacking
interactions of pyridyl rings with centroid-centroid distances of 3.937 Å exist between the
neighboring layers. In addition, strong O−H···O hydrogen bonds of the coordinated water
molecules and protonated carboxylate O atoms in collaboration with π···π stacking serves to
connect 2D sheets of 2 into a 3D supramolecular framework (Figure 2e-f). Corresponding
hydrogen bonding distances and angles are listed in Table S2. For better insight into this intricate
net of the 2D coordinating polymer, a topological analysis of compound 2 was performed. It’s
structure consists of layers parallel to (001) with a thickness of
9.22 Å andcan also be simplified to simple node-and-linker net using topology approach. The
CP 2 structure could simplify as a 3,5-c net with stoichiometry (3-c)(5-c); 2-nodal net characterized
2
7
2
by {4 .6 .8}{4 .6} point symbol (Figure 4b).
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1
1
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2
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2
2
2
2
2
2
2
3
3
3
3
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3
3
3
3
4
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4
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5
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0
1
2
3
4
5
6
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8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 2. (a) Coordination environment of the Ce(III) cation in 2. (b, c and d) Fragment of the 2D coordination
polymer grid of 2. (e, f) Fragment of the 3D supramolecular framework of 2.
Crystal structure of 3. MOF 3 crystallizes in the tetragonal non-centrosymmetric space group
P4 2 2 and the asymmetric unit contains two crystallographically independent Ce1 and Ce2
3
1
2-
centers, two pydc ligands, one and half of coordinated water, one half of coordinated nitrate ion
and four halves of non-coordinated water molecules that are disordered (Figure 3a). The Ce2 center
is found on a special position (2-fold axis), while the nitrate anion is observed in half occupancy.
In 3, the Ce1 is eight-coordinated whereas the Ce2 is nine-coordinated similar to those in 1 and 2.
2-
The Ce1 coordinates to five pydc ligands and statistically to one nitrate anion or water molecule
2
-
to form the overall 8-coordinate local geometry of the metal center. Three pydc units are bound
2
-
to the Ce(III) ion though a single carboxylate oxygen atom. The two other pydc ligands are bound
to the Ce1 center in a bidentate mode via a carboxylate oxygen atom and pyridine nitrogen atom.
A nitrate anion or a water molecule (both with the occupation factor of 0.5) is bound to complete
2
-
the coordination sphere of the Ce1 (CeO N ) (See Figure 3b). The Ce2 coordinates to four pydc
6
2
in a monodentate fashion through a single oxygen atom of carboxylate groups and two other pydc2-
in a bidentate mode via their carboxylate groups. Finally, one oxygen atom of a water molecule is
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coordinated to complete the nine-coordination of the Ce2 (CeO ) (Figure 3b). As it can be seen in
9
2
-
scheme 1e and 1f, in compound 3 again two different coordination modes of pydc are observed,
which are coordinated to 4 and 4 separate Ce(III) ions respectively. Viewing down the b-axis
shows that the Ce1 and Ce2 centers are connected through bridging carboxylate groups to form
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
the overall 3D network consisting of a helical channel with diagonal distance of 9.630 × 9.630 Å2
determined via the Ce ions distance (Figure 3c-d). Disordered water molecules as solvent
molecules that have been localized, as well as disordered nicotinamide molecules, highly
disordered, which have not been modeled, fill the channels in the structure. Note that due to the
wavelike structure, the channels are not elongated. The porosity of MOF 3 was confirmed by N2
adsorption isotherm. In order to better identify the intricate net of the 3D MOF, suitable connectors
can be defined by using topological approach. As exhibited in Figure 4c Ce ion (pink) is regarded
2-
as a node and each pydc ligand serves as a linker, MOF 3 could simplify as a 8-c net (uninodal
6
16
6
net) characterized by {3 .4 .5 } point symbol.
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1
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1
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2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
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5
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5
5
5
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5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 3. (a) Asymmetric unit of 3. (b) Coordination environment of Ce1 and Ce2. (c) Fragment of the 3D network
of 3. (d) View of helical channel in 3.
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1
1
1
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1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
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5
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5
5
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5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 4. View of (a) the 3-c net topological structure of 1, (b) the 3,5-c net with stoichiometry (3-c)(5-c) of 2 (color
-
2-
codes: blue codes represent the center ring of the 3-connected Hpydc and pydc ligands and pink codes represent
Ce3+ ions) and (c) the 8-c net topological structure of 3.
The adsorption characteristics of the frameworks in MOF 3 was investigated, and its porosity was
confirmed by the N and CO adsorption isotherms at 77 and 298 K, respectively. As demonstrated
2
2
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1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
in Figure 5, after desolvation the framework maintains a permanent porosity and exhibits a
2
-1
3
-1
Langmuir surface area (Slang) of 310 m g with a pore volume of 0.15 cm g . Gas adsorption
measurement at 1 bar was performed to investigate the CO uptake capacities of 3, which is shown
2
in Figure S4 in Supporting Information. After activation at 120 °C under vacuum overnight, the
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
-1
adsorption capacities of MOF 3 for CO was 0.81 mmol g at room temperature.
2
Figure 5. Nitrogen sorption isotherm of MOF 3.
The 1D Compound 1 is formed by refluxing the reaction mixture, while the same reaction mixture
under hydrothermal condition resulted in the 2D structure 2. This may be due to the higher reaction
temperature in the closed system which plausibly leads to various coordination modes of the pydc
ligand. Furthermore by adding the nicotinamide to the identical reaction mixture under the same
conditions as material 2 the 3D compound 3 is obtained. Although the nicotinamide ligand does
not coordinate to the Ce centers, it can facilitate the coordination of pydc to the metal centers
through deprotonating 2,4-H pydc and also via non-covalent interactions. From these observations
2
it can be concluded that the applied reaction conditions have a direct impact on the obtained
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structures. Furthermore, an ancillary ligand can conduct the obtained product to a specific structure
even without being in the final framework.
So far there are a few reported lanthanide-based coordination polymers using 2,4-H pydc as the
2
ligand43-46. However, these structures are bimetallic or oxalate was used as the ancillary ligand. To
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
the best of our knowledge, the only Ce-based coordination polymer with 2,4-H pydc ligand is
2
4
7
reported by Lush et. al. In this compound, the Ce(III) cation is nine-coordinated (CeNO ) and
8
formed by three pydc anions, one oxalate anion, and three water molecules. The oxalate and pydc
ligands bridge the Ce(III) cations, forming a two-dimensional coordination polymer. The pydc2-
ligand acts as a tetradentate bridging ligand similar the coordination mode observed in our 1D
coordination polymer (scheme 1b) and is coordinated to one Ce(III) in a bidentate fashion through
the pyridine nitrogen atom and a carboxylate oxygen atom and two more Ce(III) ions in a
monodentate fashion through single carboxylate oxygen atoms.
Catalytic acetalization reaction. Lewis acid metal sites are known to promote the acetalization
reaction of aldehydes.48-50 Therefore, the catalytic activity of MOF 3 was investigated for the
acetalization reaction of benzaldehyde and methanol as model reactants. The obtained results are
given in Table 2. In the presence of benzaldehyde and methanol as the substrates and MOF 3
catalyst, a good conversion of 80% with 99% selectivity towards benzaldehyde dimethyl acetal as
the desired product was observed. In order to clarify the general applicability of the MOF 3
catalyst, various substrates and different alcohols such as ethanol, ethylene glycol and 1,3-
propanediol were tested and the obtained results are listed in Table 2. In general, the catalyst
showed a good activity for all types of examined substrates as well as complete selectivity towards
the correspondent product. Additionally, the catalytic activity of compound 1 (1D) and compound
2 (2D) were investigated for the acetalization reaction of benzaldehyde and methanol under the
same reaction conditions. The catalysts showed good catalytic activity with conversions of 82 and
8
3% respectively (Table 2, entry 2 and 3).
5
1
Based on the work of Kanai and coworker the possible reaction mechanism is illustrated in Figure
S7. As shown, the removal of water molecules of the framework creates open coordination sites
capable of attaching to organic molecules. Hereafter, the interaction of both benzaldehyde and
methanol with the Ce center and coordinated oxygens can facilitate the nucleophilic addition of
the OH group in methanol on the carbon atom of the aldehyde group in benzaldehyde to give the
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2
2
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2
2
2
2
2
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hemiacetal derivative analogous. Afterward, the hemiacetal reacts with another methanol
molecule, most likely with the assistance of the Ce-MOF catalyst, to give the corresponding acetal
derivative.
The recyclability of MOF 3 was examined after separation of the catalyst from reaction mixture
at the end of the reaction. The recovered catalyst was reused at least 3 times for the acetalization
reaction of benzaldehyde with methanol and the obtained results are given in Figure S5. As can be
observed, the recovered MOF 3 maintains similar activity after 3 recycles. Further evidence of the
stability of the catalyst was confirmed by PXRD analysis after 3 times reuse (Figure S6).
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
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8
9
0
1
2
3
4
5
6
7
8
9
0
Table 2. Catalytic performance of the MOF 3 catalyst towards the acetalization reaction of various benzaldehyde
derivatives with alcohols.
Entry
Benzaldehyde derivatives
Alcohol
Product
1
CH
CH
CH
CH
CH
CH
CH
3
OH
OH
OH
OH
OH
OH
OH
2a
3b
4c
3
3
3
3
3
3
5c
6c
7c
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8d
CH CH OH
3
2
9e
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
0f
Reaction conditions: 0.33 mmol benzaldehyde, 0.008 mmol catalyst (10 mg), 0.5 ml methanol, 0.2 mmol dodecane,
4
0 °C, 24 h, Conversions are determined based on GC-MS. Selectivity is towards the related acetal. Conversion and
a
selectivity are reported respectively in parenthesis. Compound 1 (1D) was used as the catalyst (0.008 mmol, 4.3
b
c
d
e
f
mg). Compound 2 (2D) was used as the catalyst (0.008 mmol, 4 mg). 60 °C. Ethanol, Ethylene glycol and
,3-Propanediol were used as the solvent, respectively.
1
CONCLUSION
In summary, we have developed three new 1D, 2D and 3D Ce(III)-based frameworks by small
changes in the synthetic routs. The obtained results revealed the importance of the reaction
conditions as well as the ancillary ligand for the preparation of distinctive structures and the effect
on the properties of the materials. This shows that the lanthanide ions do not have the preference
for a specific coordination geometry because of their valence orbitals which are buried inside.
Therefore the nature of coordination modes in lanthanide ions is controlled by a subtle interplay
between metal-ligand and interligand steric interactions depending on the reaction conditions.
These findings demonstrate that Ce(III) ions are outstanding candidates to adopt distinct
coordination environments due to their adjustable coordination modes which is an important step
towards the design of Ce(III)-based frameworks for more specialized applications. The MOF 3
showed good activity and selectivity in acetalization reaction and could be recycled without loss
of activity or selectivity.
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2
2
2
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3
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Supporting Information
Selected bond lengths [Å] and angles [°] for 1, 2 and 3, Hydrogen bonds geometry, catalyst
characterizations including DRIFT spectra, TGA, XRD, CO sorption, recycling studies, proposed
2
reaction mechanism and GC-MS spectra. Tables S1-S2 and Figures S1-S7.
0
1
2
3
4
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9
0
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9
0
Acknowledgements
The authors thank the University of Gent for all the supports. PGD and SA gratefully
acknowledges the financial support from the Research Foundation Flanders (FWO-Vlaanderen)
grant No. G000117N. SA acknowledges the financial support from the Ghent University BOF
doctoral grant 01D04318. KVH thanks the Special Research Fund (BOF) – UGent (project
01N03217) for funding. RVD thanks the Hercules Foundation (project AUGE/09/024 “Advanced
Luminescence Setup”) for funding. KVH and RVD thank the Hercules Foundation (project
AUGE/11/029 “3D-SPACE: 3D Structural Platform Aiming for Chemical Excellence”) for
funding.
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chemoselective
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For Table of Contents Use Only
Ce(III)-based Frameworks: From 1D Chain to 3D Porous Metal-Organic
Framework
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*
a,b†
a†
a
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Parviz Gohari Derakhshandeh
, Sara Abednatanzi , Karen Leus , Jan Janczak , Rik Van
d
a
*b
Deun , Pascal Van Der Voort , Kristof Van Hecke
Three new 1D, 2D and 3D Ce(III)-based frameworks were developed by small changes in the
synthetic routs. Lanthanide ions are outstanding candidates to adopt distinct coordination
environments due to their adjustable coordination modes which is an important step towards the
engineering of Ln-based frameworks for more specialized applications.
ACS Paragon Plus Environment
25