Discovery of Polyoxo-Noble-Metalate-Based Metal-Organic Frameworks

Article abstract of DOI:10.1021/jacs.8b13397

Here we report on the synthesis, structure, and characterization of the first example of a polyoxopalladate (POP)-based metal-organic framework (MOF). This novel class of materials comprises discrete polyoxo-13-palladate(II) nanocubes [Pd₁₃O

Full text of DOI:10.1021/jacs.8b13397

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Discovery of Polyoxo-Noble-Metalate-Based Metal-Organic Frameworks
Saurav Bhattacharya, Wassim W. Ayass, Dereje H. Taffa, Andreas Schneemann, A. Lisa
Semrau, Suttipong Wannapaiboon, Philipp J. Altmann, Alexander Pöthig, Talha Nisar, Torsten
Balster, Nicholas C. Burtch, Veit Wagner, Roland A. Fischer, Michael Wark, and Ulrich Kortz
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b13397 • Publication Date (Web): 02 Feb 2019
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Discovery of Polyoxo-Noble-Metalate-Based Metal-Organic
Frameworks
Saurav Bhattacharya,a Wassim W. Ayass,a Dereje H. Taffa,b Andreas Schneemann,c A. Lisa Semrau,c
Suttipong Wannapaiboon,c Philipp J. Altmann,c Alexander Pöthig,c Talha Nisar,d Torsten Balster,d
Nicholas C. Burtch,e Veit Wagner,d Roland A. Fischer,c Michael Wark,b and Ulrich Kortz*a
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aDepartment of Life Sciences and Chemistry, Jacobs University, Campus Ring 1, 28759 Bremen, Germany. E-mail:
u.kortz@jacobs-university.de
bInstitute of Chemistry, Carl von Ossietzky University Oldenburg, 26129 Oldenburg, Germany
cTechnical University of Munich, Lichtenbergstraße 4, 85748 Garching, Germany
dDepartment of Physics and Earth Sciences, Jacobs University, Campus Ring 1, 28759 Bremen, Germany
eSandia National Laboratories, Livermore, California 94551, United States
*Supporting Information
their low surface areas, catalytic leaching and poor recyclability
due to their high solubility.
ABSTRACT: Here we report on the synthesis, structure and
characterization of the first example of a polyoxo-noble-metalate-
based organic framework. This novel class of materials comprises
MOFs are an important class of materials that are characterized
by ordered periodic networks of molecular components (metal
ions or clusters) that are interconnected in three dimensions by
organic linkers leading to stable framework structures with
accessible cavities or pores.[10] The tunable nature of MOFs have
made them promising candidate materials for use in the areas of
heterogeneous catalysis, gas storage and separation, drug delivery
etc.[10] Some MOFs have been reported containing conventional
heteropolytungstates or –molybdates in the cavities.[11]
discrete
polyoxo-13-palladate(II)
(POP)
nanocubes
[Pd13O8(AsO4)8H6]8- decorated by four Ba2+ ions on each of two
opposite faces. These secondary building units (SBUs) are linked
to each other via rigid linear organic groups, resulting in a stable
3D polyoxopalladate-metal organic framework (POP-MOF). This
novel material exhibits interesting sorption properties as well as
catalytic activity.
Based on all of the above, we decided to synthesize stable
heterogeneous MOF-type catalysts by using POPs as secondary
building units (SBUs). In this work, we have successfully isolated
for the first time a stable POP-based MOF material (POP-MOF),
[Pd13Ba8O8(CPA)8](NO3)2·3NaCH3COO· 2NaNO3·70H2O (JUB-
1, CPA = p-carboxyphenylarsonate) that exhibits interesting
sorption properties and heterogeneous catalytic activity in
microwave assisted Suzuki-Miyaura C – C coupling reactions.
Polyoxometalates (POMs) are a unique class of discrete,
anionic metal oxides, which are generally constructed by early d-
block elements such as tungsten, molybdenum, and vanadium in
high oxidation states (+4, +5, +6).[1] POMs are good prospects in
the areas of catalysis, molecular electronics, magnetism, and bio-
medicine due to their unique structural/compositional variety and
high thermal stability, combined with the ability to undergo multi-
electron redox transformations under mild conditions.[2] Noble
metals, such as palladium have shown immense promise as
catalysts for many industrially relevant chemical processes.[3] In
2008 Kortz’s group discovered the first polyoxopalladate (POP)
and by now >70 members are known.[4a] POPs are discrete
polyanions comprising exclusively Pd2+ addenda with external
heterogroups (e.g. AsO43-, PO43-, SeO32-) have triggered immense
interest among researchers worldwide due to their structural and
compositional novelty, stability in solution and applicability as
noble metal-based catalysts.[4]
POPs can be mainly subdivided in two structural categories: the
nanocube [MPd12O32L8]n- and the nanostar [MPd15O40L10]n- (M =
central Pd or guest metal ion, L = heterogroup cap).[4a,5] Recent
findings illustrate the structural tuning of these POPs that are
accompanied by changes in the central guest ion M,[5d,6] as well as
the ability to synthesize mixed noble metal POPs.[7] POPs exhibit
immense potential as homogeneous catalysts in the oxidation of
alcohols, hydrogenation of olefins and water oxidation.[4a,5a,8,9] In
spite of this, the applicability of these materials is hampered by
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Figure 1. (a) The polyoxo-13-palladate nanocube [Pd13O8(AsO4)8H6]8-
(Pd13As8)[4b] (b) Use of p-carboxyphenyl-arsonic acid (CPA) as capping
group allows to construct an externally functionalized nanocube,
[Pd13O8(CPA)8]14- (Pd13(CPA)8), which can act as SBU for the
construction of 3D MOF-type architectures (this work).
which is further connected to eight other such units by the CPA3-
linkers (Figure 2b) to form a 3D cationic open framework with
channels along the crystallographic ‘a’ direction (Figure 2c) that
accommodate the nitrate counter anions and guest molecules. The
channels are ~1.2 nm in diameter. The overall structure of JUB-1
can be visualized as a body-centered cubic (bcc) arrangement
(Figure 2d).
Cuboid-type POPs, such as the first member ever discovered,
[Pd13O8(AsO4)8H6]8- (Pd13As8),[4b] comprise a central Pd2+ ion
surrounded by a distorted cuboctahedral Pd12 cluster, which is
capped by eight arsonate groups forming a distorted cubic shell.
Thus, the POP nanocubes have eight latent points of extension in
three-dimensional space through the arsonate caps (Figure 1a).
Therefore, we envisaged that if we could make use of this fact and
connect Pd13As8 with rigid linear organic linkers such as p-
carboxyphenyl-arsonate ((OOC-C6H4-AsO3)3-, CPA), wherein the
arsonate group would cap the eight corners of the 13-palladate
cube and the carboxyl group in the para position would
coordinate with other metal ions, we might be able to isolate an
eight-connected 3D open framework (Figure 1b).
Powder X-ray diffraction studies (PXRD) on the as-synthesized
JUB-1 indicated that the bulk material obtained was phase-pure as
it matched with the simulated PXRD pattern (as obtained from
Mercury software version 3.8), (Figure S4). Upon dehydration of
Figure 2. (a) (left figure) The POP nanocubes in JUB-1 connected to two
pairs of tetranuclear Ba2+ clusters on opposite faces (Ba = orange balls,
arsonate caps = green balls, oxygen = red balls). The overall SBU can be
visualized as a hexadecahedron (right figure) (b) The SBU connected to
eight other SBUs through the CPA3- anions. (c) The 3D structure of JUB-
1 showing channels along the crystallographic ‘a’ direction. d) The bcc
topological framework in JUB-1.
In this endeavor, we synthesized CPAH3 using a modified
procedure (see ESI) [12] and reacted it with Pd(OAc)2 in a sodium
acetate solution (0.5 M, pH 7) at 50 ºC, maintaining the pH at
~8.2 in-between with aq. NaOH and subsequently layering the
resulting solution with aq. Ba(NO3)2 solution. After a few days,
red block crystals of JUB-1 were isolated, which were washed
with cold water and acetonitrile and air dried (~55% yield based
on Pd). Single crystal X-ray diffraction revealed that the
asymmetric unit of JUB-1 is made up of five crystallographically
distinct Pd2+ ions, two CPA3- moieties, two Ba2+ ions and two μ4-
O atoms, which leads to a cationic framework [Pd13Ba8(μ4-
O)8(CPA)8]2+ (Figures 2 and S1), the charge being balanced by
two extra-framework nitrate anions (as calculated from elemental
analysis). The twelve outer Pd2+ ions of each nanocube possess
the expected square-planar coordination geometry, being bridged
by two μ4-O2- ions and two oxygens of the arsonate group of
CPA3-, resulting in a distorted cuboctahedral arrangement with the
vertices of the cuboctahedron occupied by the twelve Pd2+ ions
(Pd – O = 1.965(6) – 2.060(6) Å) (Table S1). The center of the
cuboctahedron is occupied by a Pd2+ ion that is coordinated to
eight μ4-O2- ions (Pd – O = 2.329(6) – 2.380(6) Å), consistent
with earlier work.[5b] The cuboctahedron is further capped by
eight arsonate groups belonging to eight CPA3- ions resulting in a
distorted cube (with arsonates as the vertices) that encapsulates
the distorted cuboctahedron (Figure S2). One of the pairs of
opposite faces of the outer distorted cube is decorated by
tetranuclear (Ba2+)4 clusters that are connected to the cube through
coordination of the Ba2+ ions with oxygens of two adjacent
arsonate groups (Figure 2a). The Ba2+ ions are joined to each
other through μ2-H2O and μ2-O of the carboxylate group of the
CPA3- anion to form a cyclic tetranuclear cluster (Ba – O =
2.676(7) – 2.957(7) Å) (Figure S3). Thus, the composite
{Pd13As8Ba8O68} unit can be considered to be an 8-connected
SBU with 16 points of extension (hexadecahedron) (Figure 2a),
JUB-1 by heating at 50 ºC in vacuo for 4-5 hours, it was observed
from the PXRD pattern that there is partial loss of crystallinity
and the reflections become broader and shift towards higher
angles. This can be correlated with the loss of water molecules
from the pores, thereby leading to a disruption in the long range
order. Upon rehydration in an atmosphere of water vapor at room
temperature, JUB-1 regains its crystallinity and pore structure as
the initial PXRD pattern is regained (Figure S4).
Thermogravimetric analysis (TGA) studies reiterated the
observations of the PXRD analysis. The TGA curve of the as-
synthesized JUB-1 indicated an initial weight loss of ~20% that
corresponds to the loss of the 70 crystal waters (calc. ~19.8%)
(Figure S5). The dehydrated JUB-1, although retaining the overall
decomposition characteristics, did not exhibit the initial weight
loss in its TGA curve (Figure S6). Upon rehydration, the initial
shape of the TGA curve is regained demonstrating the facile
nature of the dehydration-rehydration behavior of the material.
Inspired by these observations, we performed N2, CO2 and
solvent vapor (H2O, MeOH and EtOH) sorption studies on the
dehydrated JUB-1 at 77, 195 and 298 K, respectively. However,
no N2 or CO2 uptake was observed, suggesting that activated
JUB-1 is non porous towards the two gases in the applied
pressure range (ESI, Figure S7). Water vapor sorption exhibits a
negligible water uptake until a partial pressure of 0.5 beyond
which there is significant uptake of water vapor (~1000 mL/g at
p/po = 0.95) (Figure 3a). This indicates that the pores, which
collapse after dehydration, open up at partial pressures of ~0.5 of
water vapor leading to an increased adsorption at higher
pressures.[13] Methanol and ethanol sorption isotherms exhibit a
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Also, an ICP-MS analysis on the filtrate after catalysis revealed a
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Pd content of only ~0.5 ppm, which further indicates that leaching
is negligible (ESI). Further, an elemental analysis (Pd, Ba and As)
of JUB-1 after catalysis indicated a Pd : As : Ba molar ratio of 13
: 8.4 : 8.2, which is consistent with the molecular formula of JUB-
1 (ESI). The catalyst JUB-1 also exhibited recyclability with no
significant loss in activity over four reaction cycles (Figure S9b).
Following this, various substituted bromo- and chlorobenzenes
were utilized as substrates along with phenylboronic acid to study
the scope of JUB-1 as a catalyst (Table S6). High conversions
(~88 – 100%) were observed for bromobenzenes, with those
functionalized with electron-withdrawing groups exhibiting
higher yields, as expected.[14a] For the substituted chlorobenzenes,
comparatively lower yields were observed since the activation of
C-Cl bonds is more difficult than C-Br bonds.[14a] However, a
quantitative yield was observed for the nitro-substituted
chlorobenzene (Figures S10). The catalyst was also found to be
stable as observed from PXRD, IR, XPS and TEM analysis of the
catalyst after the catalysis (Figures S4, S11, S12 and S13). The
catalytic activity was found to be comparable to other known Pd-
based catalysts under microwave conditions (ESI Table S7).
However, JUB-1 being a palladium-oxo cluster-based MOF has
the advantage over other reported catalysts of not requiring
additional support matrices in order to act as a heterogeneous
catalyst. Since Suzuki-Miyaura cross-coupling reaction involves
Pd(0) as the catalytically active site,[15a] we propose a mechanism
involving in situ partial reduction of the polypalladate moiety of
JUB-1 under the catalytic conditions (ESI Figure S14). MeOH
has been known to reduce Pd2+ to Pd(0) at high temperatures.[15b]
This was confirmed by XPS studies on JUB-1 catalyst, which
indicated a partial reduction of the palladate moieties when the
catalyst, after catalysis, was isolated and dried under vacuum.
Upon re-exposure to air, the reduced Pd centers are re-oxidized
(see XPS, ESI Figure S12). We envisage that JUB-1 is stable
enough to such partial oxidation-reductions (see PXRD, Figure
S4). Similar mechanistic observations have been reported
before.[15c-e] Thus, JUB-1 could be considered as an efficient pre-
catalyst in the Suzuki-Miyaura cross coupling reaction.[15c,f,g]
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Figure 3. (a) Water vapor adsorption-desorption isotherm of JUB-1 at 298
K. (b) Methanol and ethanol vapor adsorption-desorption isotherms of
JUB-1 at 298 K (the closed and open symbols indicate adsorption and
desorption, respectively).
similar increase in uptake at around relative humidity of 50-60%
(Figure 3b) and at a relative humidity of 95% both exhibit similar
total uptake (~130 mL/g). Significantly higher uptake value for
water vapor as compared to methanol or ethanol vapors could be
correlated to the higher polarity of water as compared to the
alcohols. Thus, the combination of PXRD and sorption results
alludes to the flexibility of the structure of JUB-1, which can be
considered to be a soft porous crystal.[13h]
In conclusion, we have isolated the first polyoxo-noble-
metalate-based MOF, with the discrete, cuboid polyoxopalladate
(POP) Pd13 as key building block (SBU). To date, the number of
MOFs based on noble metals (e.g. Pd) is very small, which
highlights the importance of our work.[16] This work represents
the discovery of a fundamentally novel class of materials that
paves the way for the full utilization of the entire class of discrete
polyoxopalladates (POPs), as well as polyoxoaurates, of different
shape, size, and composition,[4-7] as building blocks for stable 3D
framework materials.
Pd2+-based salts or complexes and Pd2+/Pd0 supported on
porous matrices have been extensively utilized in recent years as
homogeneous and heterogeneous catalysts, respectively, for C-C
coupling reactions.[14] Having made a MOF purely based on Pd2+
oxo-clusters as the SBU (JUB-1), we endeavored to investigate
the heterogeneous catalytic activity in the Suzuki-Miyaura cross
coupling reaction. In a typical reaction, an oven-dried microwave
reaction vessel was charged with the aryl halide (0.5 mmol,
limiting reagent), phenylboronic acid (0.75 mmol), anhydrous
K2CO3 (1.5 mmol), dehydrated JUB-1 (2 mol% Pd basis), dry
DMF (3mL) and dry MeOH (1mL). The vessel was purged with
N2 for a few minutes, sealed and heated in a microwave reactor at
100 °C (~100 W) for 1.5 h (see ESI Tables S4 and S5 for the
optimization of the catalysis conditions). JUB-1 was found to be
active as catalyst only in the presence of polar protic solvents,
such as DMF, MeOH and EtOH (ESI). This observation can be
correlated to the PXRD and sorption studies, wherein polar protic
solvents were found to regenerate the porous crystalline nature of
JUB-1. With bromobenzene as the model substrate, quantitative
conversions were observed from GC analysis after 90 mins
without indicating any leaching in the hot filtration experiment
(Figure S8a). The UV-visible spectrum of the filtrate after
catalysis did not show any peaks corresponding to Pd2+ ions in
solution, hence indicating negligible leaching if any (Figure S9a).
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS
Publications
website
at
DOI:
.
X-ray crystallographic file in CIF format for JUB-1 (CIF)
Synthetic methods, TGA analysis, PXRD, IR spectra, XPS
spectra, TEM studies and the catalytic studies for JUB-1 (PDF)
AUTHOR INFORMATION
Corresponding Author
*u.kortz@jacobs-university.de
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
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Nadjo, L.; Ramachandran, V.; Dalal, N. S.; Antonova, N. S.; Carbó, J.
U.K. thanks the German Research Council (DFG, KO-2288/26-1),
Jacobs University, and CMST COST Action CM1203
(PoCheMoN) for support. D.T. and M.W. thank the German
Research Council (DFG) for financial support for the X-ray
diffraction setup (INST 1841154-1FUGG). Figures 1 and 2 were
generated by Diamond, Version 3.2 (copyright Crystal Impact
GbR).
J.; Poblet, J. M.; Kortz, U. Polyoxopalladates Encapsulating Yttrium and
Lanthanide Ions, [XIIIPdII12(AsPh)8O32]5− (X=Y, Pr, Nd, Sm, Eu, Gd, Tb,
Dy, Ho, Er, Tm, Yb, Lu). Chem. Eur. J. 2010, 16 (30), 9076-9085. (d)
Barsukova-Stuckart, M.; Izarova, N. V.; Barrett, R. A.; Wang, Z.; van
Tol, J.; Kroto, H. W.; Dalal, N. S.; Jiménez-Lozano, P.; Carbó, J. J.;
Poblet, J. M.; von Gernler, M. S.; Drewello, T.; de Oliveira, P.; Keita,
B.; Kortz, U. Polyoxopalladates Encapsulating 8-Coordinated Metal Ions,
[MO8PdII12L8]n− (M = Sc3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Lu3+; L =
PhAsO32–, PhPO32–, SeO32–). Inorg. Chem. 2012, 51 (24), 13214-13228.
(e) Delferro, M.; Graiff, C.; Elviri, L.; Predieri, G. Self-assembly of
polyoxoselenitopalladate nanostars [Pd15(μ3-SeO3)10(μ3-O)10Na]9− and their
supramolecular pairing in the solid state. Dalton Trans. 2010, 39 (19),
4479-4481. (f) Xu, F.; Scullion, R. A.; Yan, J.; Miras, H. N.; Busche,
C.; Scandurra, A.; Pignataro, B.; Long, D.-L.; Cronin, L. A
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