Cooperative cluster metalation and ligand migration in zirconium metal-organic frameworks

Article abstract of DOI:10.1002/anie.201505625

Cooperative cluster metalation and ligand migration were performed on a Zr-MOF, leading to the isolation of unique bimetallic MOFs based on decanuclear Zr₆M₄ (M=Ni, Co) clusters. The M²⁺ reacts with the μ₃-OH and terminal H₂O ligands on an 8-connected [Zr₆O₄(OH)₈(H₂O)₄] cluster to form a bimetallic [Zr₆M₄O₈(OH)₈(H₂O)₈] cluster. Along with the metalation of Zr₆ cluster, ligand migration is observed in which a Zr-carboxylate bond dissociates to form a M-carboxylate bond. Single-crystal to single-crystal transformation is realized so that snapshots for cooperative cluster metalation and ligand migration processes are captured by successive single-crystal X-ray structures. In³⁺ was metalated into the same Zr-MOF which showed excellent catalytic activity in the acetaldehyde cyclotrimerization reaction. This work not only provides a powerful tool to functionalize Zr-MOFs with other metals, but also structurally elucidates the formation mechanism of the resulting heterometallic MOFs. Mixed metal MOF: Cooperative cluster metalation and ligand migration were performed on a Zr-MOF, leading to the isolation of Zr₆M₄ based bimetallic MOFs (right). This strategy allows for the functionalization of Zr-MOFs with other metals for a variety of promising applications.

Full text of DOI:10.1002/anie.201505625

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Angewandte
Communications
International Edition: DOI: 10.1002/anie.201505625
German Edition: DOI: 10.1002/ange.201505625
Metal–Organic Frameworks
Cooperative Cluster Metalation and Ligand Migration in Zirconium
Metal–Organic Frameworks
Shuai Yuan, Ying-Pin Chen, Junsheng Qin, Weigang Lu,* Xuan Wang, Qiang Zhang,
Mathieu Bosch, Tian-Fu Liu, Xizhen Lian, and Hong-Cai Zhou*
[
6]
Abstract: Cooperative cluster metalation and ligand migration
were performed on a Zr-MOF, leading to the isolation of
unique bimetallic MOFs based on decanuclear Zr M (M = Ni,
moisture. Therefore, researchers in recent years have been
concentrating on the development of Zr-MOFs, which tend to
possess much greater stability through the strength of ZrÀO
6
4
2
+
[7]
Co) clusters. The M reacts with the m -OH and terminal H O
bonds and high connectivity of Zr clusters. The exceptional
3
2
6
ligands on an 8-connected [Zr O (OH) (H O) ] cluster to
chemical stability of Zr-MOFs has made them a suitable
6
4
8
2
4
[8]
form a bimetallic [Zr M O (OH) (H O) ] cluster. Along with
platform for the investigation of various applications. Yet,
the underlying functionality of Zr-MOFs is less diversified as
opposed to low-valent-metal based MOFs. First, the open
metal sites in many Zr-MOFs are not accessible to guest
molecules, which diminishes their potential in gas-storage
applications, as open metal sites are deemed to be a significant
6
4
8
8
2
8
the metalation of Zr cluster, ligand migration is observed in
6
which a Zr–carboxylate bond dissociates to form a M–
carboxylate bond. Single-crystal to single-crystal transforma-
tion is realized so that snapshots for cooperative cluster
metalation and ligand migration processes are captured by
3
+
[9]
successive single-crystal X-ray structures. In was metalated
into the same Zr-MOF which showed excellent catalytic
activity in the acetaldehyde cyclotrimerization reaction. This
work not only provides a powerful tool to functionalize Zr-
MOFs with other metals, but also structurally elucidates the
formation mechanism of the resulting heterometallic MOFs.
contributor to the gas adsorption enthalpy. Second, multiple
redox states are responsible for many catalytic properties; the
catalytic reactions driven by Zr-MOFs are largely restricted
within Lewis acid catalysis because of the redox inert nature
4
+ [10]
4+
of Zr . In addition, the diamagnetic property of Zr also
limits its magnetic applications.
Efforts have been made to functionalize Zr-MOFs with
other transition metals by incorporating the active metal
species on the nodes of Zr-MOFs. An intuitive approach is to
directly construct a MOF from a bimetallic cluster which
contains zirconium as structural support and other transition
metals as active sites. The one pot synthesis of bimetallic M-
Zr-MOFs (M = 3d metal) has been attempted extensively by
us but to no avail. As an alternative approach, bimetallic
MOFs can be realized by post-synthetic metal exchange or
T
ransition-metal cluster complexes have been widely studied
for their structures, bonding interactions, and applications in
[1]
catalysis and magnetism. Recently, heterometallic multi-
nuclear clusters have attracted increasing attention owing to
the interesting ligand dynamics and synergistic effects
between different metal species. Compared to the conven-
tional metal oxide mixtures, the stoichiometry of metal
species in heterometallic clusters can be controlled on the
atomic scale. However, when deposited onto porous supports,
aggregation of these nanoclusters often occurs at elevated
temperatures. Thus, it is urgent to discover new materials
with well-separated nanoclusters and controllable stoichiom-
etry of metal species on the molecular level. In this sense,
metal–organic frameworks (MOFs) constructed with isolated
metal clusters and organic struts are ideal candidates for the
employment of heterometallic clusters. Divalent-metal-
containing MOFs have been extensively studied for their
exceptional porosity and potential applications in gas storage/
[
2]
metalation of Zr cluster. Cohen and co-workers reported
6
a titanium-containing analogue of UiO-66 (Ti-UiO-66) syn-
[
3]
4+
thesized by post-synthetic metal exchange of Zr with
4
+ [11a]
Ti ,
which was later on revealed to exhibit photocatalytic
[11b–d]
activity.
The Hupp group demonstrated that the -OH
ligands on the Zr nodes of UiO-66 can be metalated with
6
5
+
[12a]
redox-active V ions to produce V-UiO-66 for catalysis.
Gas-phase atomic layer deposition has also been adopted in
a Zr-MOF, Nu- 1000, to introduce Zn and Al to the Zr6
[
4]
2
+
3+
[12b]
nodes.
However, despite all these efforts, it is still an
[4b, 5]
separation, catalysis and magnetics.
tical applications are hampered by their sensitivity to ambient
However, their prac-
elusive goal to obtain the precise structural information of
post-incorporated metal centers because of the disordered
distributions and low occupancy of the post-synthetically
incorporated metal ions.
[
*] S. Yuan, Y.-P. Chen, Dr. J. Qin, Dr. W. Lu, X. Wang, Dr. Q. Zhang,
M. Bosch, Dr. T.-F. Liu, X. Lian, Prof. Dr. H.-C. Zhou
Department of Chemistry
Single-crystal X-ray diffraction (SCXRD) is a powerful
and ubiquitous technique to definitively elucidate structures
Texas A&M University
College Station, TX 77843 (USA)
E-mail: weiganglu@yahoo.com
zhou@chem.tamu.edu
Homepage: http://www.chem.tamu.edu/rgroup/zhou/
[13]
at the molecular level. It has been widely used to determine
static structures as well as provide direct evidence of
consecutive chemical transformations. Utilizing this tech-
nique, Doonan and co-workers have recently been able to
solve the precise coordination environments of metals on
Supporting information and ORCID(s) from the author(s) for this
article are available on the WWW under http://dx.doi.org/10.1002/
anie.201505625.
[14]
metallo-linkers in MOFs. This prompted us to study the
cluster transformation during the metalation in a crystalline
1
4696
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À
Zr-MOF matrix via SCXRD. Herein, we report the synthesis
of two bimetallic MOFs by performing post-synthetic cluster
metalation on PCN-700, a Zr-MOF with 8-connected [Zr O -
-OH /H O ligands poised for post-synthetic metalation (Fig-
2
À
ure 1c). Second, the reactive terminal -OH /H O ligands are
2
directly exposed to the channels which facilitates metal ion
diffusion and thus the metalation reaction. Third, PCN-700
possesses a certain degree of structural flexibility, which
endows the framework with structural adaptability during the
metalation. In addition, PCN-700 is robust enough to main-
tain crystallinity during the metalation under solvothermal
conditions, which enables us to employ single-crystal X-ray
diffraction (SCXRD) to monitor the transformation process.
Overall, the reduced connectivity, accessibility, flexibility, and
high stability make PCN-700 an optimal platform for
implementing the post-synthetic cluster metalation strategy.
To carry out the post-synthetic cluster metalation, PCN-
700 crystals were exposed to a DMF (N,N-dimethylforma-
mide) solution of Ni(NO ) at 858C for 48 h. The shape and
size of PCN-700 crystals were maintained throughout the
modification, indicating a single-crystal to single-crystal
transformation rather than dissolution and reformation of
the crystals. The resultant crystals, designated as PCN-800-
(Ni), were refined in the P4 /mmc space group. Although it
exhibits the identical topology to PCN-700 (Figure 1b), the
metal nodes and the ligand conformation have undergone
6
4
(
OH) (H O) ] clusters. SCXRD unambiguously shows that
8 2 4
a [Zr M O (OH) (H O) ] (M = Co, Ni) cluster is formed as
6
4
8
8
2
8
2+
À
a result of the reaction between M (M = Co, Ni) and OH /
H O ligands on the [Zr O (OH) (H O) ] cluster. Interest-
2
6
4
8
2
4
ingly, ligand migration is observed concurrently with cluster
metalation, in which the ligand dissociates itself from the
vertex zirconium atom and bonds to the post-incorporated
metal. Single crystallinity is preserved throughout the process
so that the structural transformation is recorded by successive
SCXRD measurements. As post-synthetic cluster metalation
could occur on Zr clusters with reduced connectivity, we
6
believe that it is a general strategy to synthesize bimetallic
MOFs containing isolated heterometallic clusters with well-
defined structures and metal contents. We anticipate that
cluster metalation will offer broad opportunities for a variety
of applications including catalysis, gas adsorption, and
magnetics. This work also sheds light on the possible
mechanism of the cluster transformation process, which is of
great importance for the design of functionalized MOFs with
high chemical stability.
3
2
2
2
+
A Zr-MOF, PCN-700, was chosen as a scaffold structure to
dramatic changes. Each Ni reacts with two terminal -H O
ligands and one m -OH ligand in a Zr cluster to afford a new
Zr Ni cluster. Interestingly, a ligand migration is concur-
2
[15]
build bimetallic MOFs (Figure 1a). PCN-700 matches up
with four criteria for post-synthetic cluster metalation studies.
First, as opposed to the 12-connected Zr-cluster in the UiO
series, the [Zr O (OH) (H O) ] cluster in PCN-700 is 8-
3
6
6
4
rently observed during the cluster metalation which involves
the dissociation of Zr-carboxylate bond and formation of Ni-
carboxylate bond. As a result, the carboxylate ligand migrates
from Zr clusters to the expanded Zr Ni clusters and bridges
6
4
8
2
4
connected with carboxylate ligands, leaving eight terminal
6
6
4
2+
4+
2+
a Ni and a Zr (Figure 1c,d). Each Ni is 6-coordinated
with one m -O, two m -OH, one terminal -H O, and two O
4
3
2
atoms from carboxylates, completing an octahedral geometry.
4+
Two kinds of crystallographically independent Zr ions exist
within the Zr Ni cluster. The coordination environments of
6
4
4+
four equivalent Zr ions on the equatorial plane are intact
during the cluster metalation and ligand migration, whereas
4+
two Zr ions at axial positions become 6-coordinated with
two m -O, two m -O, and two terminal -H O. The Zr–O and Ni–
4
3
2
O distances, ranging from 2.03 Š to 2.25 Š and 1.94 Š to
[7c,16]
2
.07 Š, respectively, fall within the normal range.
In stark
contrast to other metal exchanged or metalated Zr-MOFs (i.e.
[11a,12]
Ti-UiO-66 and V-UiO-66),
PCN-800(Ni) is formed
through the cleavage of Zr–carboxylate bonds and generation
of Ni–carboxylate bonds. Consequently, PCN-800(Ni) is
a fundamentally new structure with well-defined Zr Ni
6
4
clusters. To our knowledge, a bimetallic zirconium-containing
MOF with Zr M (M = transition metal) nodes has not been
6
4
reported before.
Given that PCN-700 could undergo cluster metalation and
ligand migration with retention of single crystallinity, we
turned our efforts to obtaining SCXRD data for the
intermediates during the transformation process. Single
crystals of PCN-700 were immersed in a DMF solution of
Ni(NO ) at 858C and sampled every 2, 4, 6, 12, and 24 h. The
samples were analyzed by single-crystal X-ray diffraction
which gave snapshots of the structure transformation process.
The SCXRD data clearly reveals a cooperative cluster
metalation and ligand migration process. As shown in Fig-
Figure 1. a) The structure of PCN-700; b) the structure of PCN-800-
3
2
(
Ni); c) the Zr cluster in PCN-700; d) the Zr Ni cluster in PCN-
6
6
4
8
00(Ni) showing the incorporated Ni and migrated carboxylate
ligands; e) the ligand conformation in PCN-700; f) the ligand confor-
mation in PCN-800, see text for details. pink Ni; blue Zr; red O;
black C; H atoms are omitted for clarity.
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whereas the -OH and carboxyl-
ate ligands changed their coor-
dination modes to accommo-
date the post-incorporated
[
16]
metals. The resulting hetero-
metallic clusters can also be
characterized by SCXRD, but
the transformation process
remains unclear because of the
difficulties in capturing the
[16]
intermediates.
In our work,
however, the crystalline MOF
provides a perfect platform to
enable us to, for the first time,
structurally elucidate the inter-
mediate clusters by SCXRD
and therefore garner funda-
mental insights into the metal-
ation process.
We propose that the depro-
Figure 2. Cluster transformation during the cluster metalation and ligand migration; the yellow arrows
illustrate the metal migration and green arrows the ligand migrations.
tonation of terminal -H O and
2
m -OH ligands on Zr clusters is
3
6
directly correlated to the metal-
2
+
ure 2b, the Ni ions first attach to two terminal -H O. The
ation. According to previous research, [Zr (m -O) (m -OH) -
2
6
3
4
3
4
2+
four disordered Ni ions are observed on each Zr clusters
with occupancy of 12.5%, indicating that 0.5 Ni is coordi-
nated to each Zr cluster on average. With increased soaking
(OH) (OH ) (COO) ] is the preferred form for 8-connected
4 2 4 8
6
2+
[17]
Zr clusters (Figure 3a). The terminal -H O is first depro-
6 2
+
2
tonated and coordinated to Ni ions (Figure 3b). Then, the
6
2+
2+
time, the attached Ni ion further coordinates with m -OH so
m -OH is deprotonated and coordinated to the same Ni , so
3
3
2
+
2+
that each Ni is chelated by a m -O and two terminal -OH
that this Ni is fixed by two m -OH and one m -O (Figure 3c).
3
3
4
ligands (Figure 2c). An intermediate is observed in which
Overall, four terminal -H O ligands are deprotonated to form
2
2+
2
0% of Ni is attached to terminal -OH ligands and 80% of
four m -OH, meanwhile four m -OH ligands are deprotonated
3
3
2+
Ni is chelated by a m -O and two terminal -OH ligands
into m -O. The eight negative charges from deprotonation are
3
4
(
Figure 2c). The ligand migration process occurs along
2+
with the cluster metalation. When 1.15 Ni is incorpo-
rated in each Zr cluster at 6 h, only a negligible amount
6
2+
of ligand migrates. At 12 h, the occupancy of Ni
reaches 46% (corresponding to 1.84 Ni per Zr6
cluster) and ligand migration becomes obvious. The
2+
2
+
site occupancy of Ni reaches almost 100% after 24 h,
meanwhile, we are able to observe an intermediate in
which half of the ligand migrates. At this stage, the unit
cell is doubled compared to PCN-700 because of the
decreased symmetry upon ligand migration. Eventu-
ally, when the ligand migration completes, the unit cell
goes back to its original state. As a result, a MOF based
on [Zr Ni O (OH) (H O) ] clusters is generated. The
6
4
8
8
2
8
structural transformation of bulk material was charac-
terized by powder X-ray diffraction. It is observed that
the peaks at around 78 and 108 gradually split with the
incorporation of Ni because of the reduced symmetry,
which matches well with the simulations (Figure S3–S8
in the Supporting Information). The bulk materials at
each transformation stage have the same composition
as single crystals, which was substantiated by energy
dispersive X-ray analysis and inductively coupled
plasma mass spectrometry (Table S3). It should be
noted that the cluster metalation by 3d metal cations
have been reported in isolated Zr cluster in which the
6
Figure 3. Cluster metalation showing the incorporation of Ni; red indicates the
robust Zr clusters remained during the transformation deprotonated ligands.
6
1
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2
+
balanced by four post-incorporated Ni ions (Figure 3 f).
DMF gradually decomposes into dimethyl amine at high
temperature in the presence of transition-metal ions, which
we believe is responsible for the deprotonation of terminal
this strategy allows for the functionalization of Zr-MOFs for
a variety of promising applications.
-
H O and m -OH ligands, and thus favors the metalation Acknowledgements
2
3
process. To corroborate our hypothesis, Et N or NaOH was
3
added during the post-synthetic cluster metalation in the hope
The gas adsorption–desorption studies of this research was
supported by the Center for Gas Separations Relevant to
Clean Energy Technologies, an Energy Frontier Research
Center funded by the U.S. Department of Energy, Office of
Science, Office of Basic Energy Sciences under Award
Number DE-SC0001015. Structural analyses were supported
by Office of Naval Research under Award Number
N000141310753. We also acknowledge the financial supports
of ARPA-e project funded by the U.S. Department of Energy
under Award Number DE-AR0000249 and Welch Founda-
tion under Award Number A-1725. The FE-SEM acquisition
of the center was supported by National Science Foundation
Grant DBI-0116835, the Vice President for Research Office
and the Texas Engineering Experiment Station.
to speed up the deprotonation process of terminal -H O and
2
m3-OH ligands, therefore accelerate the metalation process.
As expected, with the addition of Et N or NaOH to the
3
solution, PCN-800(Ni) can be synthesized in 6 h. In parallel
work, the Hupp group very recently also proposed a similar
stepwise deprotonation mechanism of cluster metalation,
which is supported by computational results and experimental
[18]
X-ray pair distribution function (PDF) analysis.
Those
exhaustive parallel studies largely substantiate our proposed
mechanism.
The flexibility of PCN-700 plays an important role in the
ligand migration. The conformation of the ligand can undergo
dramatic change, allowing the carboxylate group to dissociate
4
+
2+
from Zr and associate with the post-incorporated Ni ion.
The torsion angle of the linker, defined by two methylphenyl
planes, changed from 82.98 in PCN-700 to 69.78 in PCN-
Keywords: cluster metalation · heterometallic MOFs ·
ligand migration · metal–organic frameworks · zirconium
8
00(Ni), as shown in Figure 1e,f. Adaptation of ligand
How to cite: Angew. Chem. Int. Ed. 2015, 54, 14696–14700
Angew. Chem. 2015, 127, 14909–14913
conformation and coordination to meet the coordination
environment of inserted metal ions has rarely been
reported.
after the transformation process as supported by powder X-
ray diffraction patterns (Figure S8) and N gas adsorption-
desorption isotherms (Figure S13). As a proof-of-concept of
the general applicability of this method, Co(NO ) was used
instead of Ni(NO ) under the same conditions, which gave
rise to a isostructural bimetallic MOF based on Zr Co4
[
19]
The bulk material maintains its crystallinity
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a model reaction, which is an industrially attractive process
that can lead to many different products (Scheme S2). As
[
[
1
InCl is known as a homogeneous catalyst for cyclotrimeriza-
3
[20]
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Please note: Minor changes have been made to this manuscript since
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