Single-Crystal-to-Single-Crystal Installation of Ln4(OH)4 Cubanes in an Anionic Metallosupramolecular Framework

Article abstract of DOI:10.1002/anie.202008296

Postsynthetic installation of lanthanide cubanes into a metallosupramolecular framework via a single-crystal-to-single-crystal (SCSC) transformation is presented. Soaking single crystals of K₆[Rh₄Zn₄O(l-cys)₁₂]

Full text of DOI:10.1002/anie.202008296

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Lanthanides
Hot Paper
Single-Crystal-to-Single-Crystal Installation of Ln4(OH)4 Cubanes in
an Anionic Metallosupramolecular Framework
Nobuto Yoshinari, Natthaya Meundaeng, Hiroyasu Tabe, Yusuke Yamada, Satoshi Yamashita,
Yasuhiro Nakazawa, and Takumi Konno*
Abstract: Postsynthetic installation of lanthanide cubanes into
a metallosupramolecular framework via a single-crystal-to-
single-crystal (SCSC) transformation is presented. Soaking
single crystals of K6[Rh4Zn4O(l-cys)12] (K6[1]; l-H2cys =l-
cysteine) in a water/ethanol solution containing Ln(OAc)3
(Ln3+ = lanthanide ion) results in the exchange of K+ by
Ln3+ with retention of the single crystallinity, producing Ln2[1]
(2Ln) and Ln0.33[Ln4(OH)4(OAc)3(H2O)7][1] (3Ln) for early
and late lanthanides, respectively. While the Ln3+ ions in 2Ln
exist as disordered aqua species, those in 3Ln form ordered
hydroxide-bridged cubane clusters that connect [1]6À anions in
a 3D metal-organic framework through coordination bonds
with carboxylate groups. This study shows the utility of an
anionic metallosupramolecular framework with carboxylate
groups for the creation of a series of metal cubanes that have
great potential for various applications, such as magnetic
materials and heterogeneous catalysts.
modification, and the incorporation and fabrication of metal
complexes or clusters in the interstices.[3–5] In contrast to the
development of PSMs in infinite porous materials, PSMs of
crystalline metallosupramolecular compounds consisting of
discrete molecules or ions are much less explored, mainly due
to the inherent weakness of their frameworks, which consist of
noncovalent interactions.[6] The limited examples involve
i) the exchange of counterions or solvents,[7] ii) the condensa-
tion of guest molecules or ions,[8,9] and iii) the coordination of
guest molecules or ions to host metal centers.[10,11]
Lanthanide clusters with bridging hydroxide groups have
received increasing attention. To date, a variety of clusters of
Lnx(OH)y with different compositions that show intriguing
photophysical, magnetic, and catalytic properties, have been
synthesized by using O- or N-donating ancillary ligands.[12–15]
However, the isolation of this class of clusters in a controlled
manner is quite difficult due to the large pH dependency,[13] as
well as the geometrical flexibility of lanthanide ions.[16] PSM is
expected to provide a promising approach to synthesizing
lanthanide hydroxide clusters, given that the spatial constraint
of the crystal framework of the host prevents the random
growth of cluster structures. In this work, we report that
lanthanide hydroxide clusters are created in an anionic
metallosupramolecular framework via the PSM approach.
As a crystalline host compound, we employed the ionic solid
K6[Rh4Zn4O(l-cys)12] (K6[1]; l-cys =l-cysteinate) bearing
free carboxylate groups, which shows superionic conduction
due to the hydrated K+ ions at room temperature.[17,18] Just by
soaking crystals of K6[1] in a solution containing Ln(OAc)3,
the K+ ions in K6[1] were replaced by Ln3+ ions to form new
crystalline products, 2Ln and 3Ln, for early lanthanides (LaIII,
CeIII, PrIII, NdIII, SmIII, and EuIII) and late lanthanides (GdIII,
TbIII, DyIII, ErIII, HoIII, TmIII, YbIII, and LuIII), respectively, in
a single-crystal-to-single-crystal (SCSC) transformation man-
ner (Scheme 1). Crystalline 2Ln was found to contain disor-
dered aqua Ln3+ ions, most of which bind to [1]6À anions
through coordination bonds. Remarkably, Ln3+ ions in 3Ln
were found to form tetranuclear cubane clusters, [Ln4(m3-
OH)4(m2-OAc)3(H2O)7]5+, which connect [1]6À anions in a 3D
MOF structure through coordination bonds. The creation of
such a series of lanthanide cubanes via an SCSC process, as
well as the SCSC transformation of an ionic solid to a MOF
structure by the exchange of counter cations, is unprecedent-
ed.
Introduction
The postsynthetic modification (PSM) of crystalline solids
has attracted the attention of synthetic chemists and material
scientists for a long time.[1–4] This is because PSM allows the
creation of new compounds and materials that are difficult to
synthesize via conventional methods.[1–3] Recently, functional
host-guest composite materials have been created using the
PSM approach.[4,5] The initial development of PSM started
with porous inorganic materials, represented by zeolites.[2]
Subsequently, it was applied to metal–organic frameworks
(MOFs), which are porous materials with infinite coordina-
tion-bonding networks.[3] It has been shown that the robust-
ness of MOFs allows small molecules or ions to penetrate
their interstices, leading to metal or ligand exchange, ligand
[*] Dr. N. Yoshinari, Dr. N. Meundaeng, Dr. S. Yamashita,
Prof. Y. Nakazawa, Prof. T. Konno
Department of Chemistry, Graduate School of Science
Osaka University, Toyonaka, Osaka 560-0043 (Japan)
E-mail: konno@chem.sci.osaka-u.ac.jp
Dr. N. Meundaeng
Department of Chemistry, Faculty of Science
King Mongkut’s Institute of Technology Ladkrabang
Bangkok, 10520 (Thailand)
Dr. H. Tabe, Prof. Y. Yamada
Graduate School of Engineering, Osaka City University
Sugimoto, Sumiyoshi, Osaka 558-8585 (Japan)
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.202008296.
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Scheme 1. Postsynthetic installation of Ln4(OH)4 cubane clusters in
the [1]6À framework.
Results and Discussion
Synthesis, Characterization, and Structure of 2La
Figure 1. Perspective views of a) the molecular structure of [1]6À
,
Freshly prepared single crystals of K6[1] (K6[Rh4Zn4O(l-
cys)12]) with a rhombic-dodecahedron shape (0.1–0.2 mm)
were soaked in a 0.02m solution of La(OAc)3 in water/ethanol
(1:3) for one week. To complete the reaction, the solution was
changed to a 0.1 aqueous solution of La(OAc)3, and the
crystals were soaked for an additional few days. While crystals
of K6[1] are highly soluble in water, the resulting crystals (2La)
are insoluble in water although their crystal shape, size, and
color do not change (Supporting Information, Figure S1),[19]
which is indicative of the SCSC transformation from K6[1] to
b) [1]6À anion (yellow) hydrogen-bonded to six adjacent [1]6À anions
(blue), c) the hydrogen-bonded framework composed of [1]6À anions
(blue), and d) the disordered aqua La ions at site A in 2La. H atoms
have been omitted for clarity. La red-purple, Rh blue, Zn dark gray,
S yellow, O pink, N pale blue, C gray. Dashed pink lines indicate H
bonds.
severe disorder.[21] In an interstitial space of the hydrogen-
bonding framework in 2La (site A), the La1B atom is located
on the crystallographic C3 axis and is surrounded by the three
disordered La1A atoms that are coordinated to three
carboxylate groups from three [1]6À complex-anions (Fig-
ure 1d). In another interstitial space (site B), both the
disordered La2A and La2B atoms are coordinated to
carboxylate groups and are located around the C3 axis
(Supporting Information, Figure S5).[19] Thus, 2La can be
described as an ionic crystal with a hydrogen-bonding frame-
work made up of [1]6À anions, the interstitial spaces of which
accommodate aqua La3+ ions to balance the charge of the
crystal (Supporting Information, Figure S6).[19]
2La. The retention of the S-bridged RhIII4ZnII octanuclear
4
structure in [1]6À in the course of the reaction was confirmed
by the infrared (IR) and diffuse reflectance (DR) spectra of
2
La in the solid-state, which are essentially the same as those of
K6[1] (Supporting Information, Figures S2, S3).[19] X-ray
fluorescence (XRF) analysis showed that 2La contains La,
Rh, and Zn atoms as metal components in a 1:2:2 ratio, and K
atoms were not detected.[19]
Single-crystal X-ray analysis revealed that the crystals of
2La belong to the cubic space group P213, which is the same as
that of K6[1].[18a,19] Consistent with this, no significant differ-
ences in the powder X-ray diffraction (PXRD) patterns of
K6[1] and 2La were observed (Supporting Information, Fig-
ure S4).[19] As shown in Figure 1a, 2La contains [1]6À complex
anions with 12 coordinated amine and 12 pendent carboxylate
groups on its spherical surface. In 2La, each complex-anion is
Synthesis, Characterization, and Structure of 3Lu
The same treatment using Lu(OAc)3 instead of La(OAc)3
also gave water-insoluble crystals (3Lu) via SCSC transforma-
tion. While the IR and DR spectral features of 3Lu are the
same as those of 2La (Supporting Information, Figures S2 and
S3),[19] XRF analysis indicated that 3Lu contains Lu, Rh, and
Zn atoms in a 1:1:1 ratio, rather than the 1:2:2 ratio seen in
2La. In addition, the intensity ratios of the diffractions in the
PXRD profile of 3Lu are different from those of 2La, especially
for the (111) and (200) indices (Supporting Information,
Figure S4).[19] Single-crystal X-ray analysis indicated that
crystals of 3Lu also belong to the cubic space group P213,
forming a 3D hydrogen-bonding framework analogous to that
À
linked to six neighboring complex-anions through N H···O
hydrogen bonds (Figures 1b), forming a 3D hydrogen-bond-
ing network with a lcy-type topology (Figure 1c).[17b,20] While
this network is the same as that in K6[1], the hydrogen bonds
in 2La (2.87–2.98 ꢀ) are longer than those in K6[1] (2.75–
2.91 ꢀ).[18a] Two aqua La3+ ions, which are positionally
disordered in four positions (La1A, La1A, La2A, and
La2A), are present per [1]6À complex-anion in 2La, consistent
with its chemical formula of La2[1]·nH2O, which was deter-
mined based on elemental analysis, although the water
molecules bound to La3+ ions were not fully located due to
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of 2La (Supporting Information, Figure S7).[19] Furthermore,
and Lu3B) exist in interstitial spaces corresponding to site B
and another site C in 2La (Supporting Information, Fig-
ure S8).[19] Furthermore, the interstices of the MOF structure
in 3Lu are occupied by a number of water molecules of
crystallization (Supporting Information, Figure S9).[19,24]
Thus, the formula of 3Lu is represented as Lu0.33[{Ln4(OH)4-
(OAc)3(H2O)7}{1}]·nH2O, which agrees well with the elemen-
tal analysis.
À
the N H···O hydrogen bonds in 3Lu (2.85–2.98 ꢀ) are similar
to those in 2La (2.87–2.98 ꢀ), despite the much smaller ionic
radius of Lu3+ (0.86 ꢀ) compared with that of La3+
(1.03 ꢀ).[16] Notably, in each interstitial space corresponding
to site A in 2La, the incorporated Lu3+ ions in 3Lu form
a tetranuclear [Lu4(OH)4(OAc)3(H2O)7]5+ cluster (Figure 2a)
with four Lu3+ atoms spanned by four m3-OHÀ ions in
a tetrahedral geometry to form a cubane-type {Lu4(OH)4}8+
core.[21] The intracluster Lu···Lu distances (av. 3.68 ꢀ) in 3Lu,
À
as well as the Lu O bond distances (av. 2.31 ꢀ), are similar to
Synthesis, Characterization, and Structures of 2Ln and 3Lu
those in discrete [Lu4(OH)4(FcacacPh)8] (av. Lu···Lu =
[22]
À
3.65 ꢀ, av. Lu O = 2.30 ꢀ), which is the only example of
Prompted by the production of 2La and 3Gd with La(OAc)3
and Lu(OAc)3, respectively, crystals of K6[1] were immersed
in an aqueous ethanol solution containing other Ln(OAc)3
species (Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and
Yb) under the same conditions. As expected, this treatment
led to the complete exchange of K+ ions in K6[1] by Ln3+ ions,
producing crystals of 2Ln (Ln = Ce, Pr, Nd, Sm, and Eu) and
3Ln (Ln = Gd, Tb, Dy, Ho, Er, Tm, and Yb) via an SCSC
process. The XRF and elemental analyses indicated that 2Ce,
2Pr, 2Nd, 2Sm, and 2Eu with early lanthanides and 3Gd, 3Tb, 3Dy,
a lutetium hydroxide cubane cluster reported thus far. In each
cubane cluster of 3Lu, the three pairs of LuIII centers
(Ln2···Ln2) in the trigonal basal plane of the LuIII tetrahe-
4À
dron are each spanned by an acetate ion (av. Lu OOAc
=
2.26 ꢀ), which appears to maintain the cubane structure.
Furthermore, the remaining three pairs of LuIII centers
(Ln1···Ln2) are each spanned by a carboxylate group of
[1]6À (Lu OCOO = 2.26 ꢀ). Thus, each cubane cluster connects
À
three [1]6À anions through carboxylate groups such that each
[1]6À anion is surrounded by three cubane clusters (Fig-
ure 2b,c). As a result, the cubane cations and the [1]6À anions
are alternately linked by COO-Lu coordination bonds to
construct a 3D MOF structure with srs-b-type topology in 3Lu
(Figure 2d).[20] In the cubane cluster of 3Lu, the Lu1 and Lu2
centers are coordinated by one and two water molecules, in
addition to carboxylate and hydroxide groups, completing 7-
coordinate face-capped octahedron and 8-coordinated do-
decahedron (Lu2) geometries, respectively (Figure 2a).[23] To
balance the charge of the crystal, disordered Lu3+ ions (Lu3A
3Ho, 3Er, 3Tm, and 3Yb with late lanthanides have the same
formulas as those of 2La and 3Lu, respectively. The former and
the latter products show PXRD features that are essentially
the same as those of 2La and 3Lu, respectively (Supporting
Information, Figure S10).[19] Single-crystal X-ray analysis
established that 2Ln (Ln = Ce, Pr, Nd, Sm, and Eu) and 3Ln
(Ln = Gd, Tb, Dy, Ho, Er, Tm, and Yb) are isostructural with
2La and 3Lu, respectively, possessing the ionic solid structure of
Ln2[1]·nH2O (Supporting Information, Figure S11) and the
3D MOF structure of Ln0.33[{Ln4(OH)4(OAc)3(H2O)7}-
{1}]·nH2O (Figures 3 and S12), respectively.[19] In 3Ln, the
averaged Ln···Ln distances in the {Ln4(OH)4}8+ cubanes
decrease in the order 3Gd (3.81 ꢀ) > 3Tb (3.79 ꢀ) > 3Dy
(3.77 ꢀ) > 3Ho (3.75 ꢀ) > 3Er, 3Tm (3.73 ꢀ) > 3Yb (3.69 ꢀ)
> 3Lu (3.68 ꢀ), in parallel with the decrease in the ionic radii
of Ln3+ owing to lanthanide contraction.[16] It appears that the
interstitial space surrounded by three [1]3À anions in the
hydrogen-bonding framework is not large enough to accom-
modate the {Ln4(OH)4}8+ cubanes containing early lanthanide
ions with larger ionic radii, with the border existing between
Eu3+ and Gd3+ ions.[25] Thus, the lanthanide ions in 2La, 2Ce, 2Pr,
2Nd, 2Sm, and 2Eu are located in the interstitial spaces as
Figure 2. Perspective views of a) the LuIII cubane cluster, b) the Lu4
4
cubane cluster connected to three [1]6À (blue), c) [1]6À bound to three
Lu4 cubane clusters, and d) the packing structure in 3Lu. H atoms
except for cubane clusters in (a) and (b) have been omitted for clarity.
Lu dark red–purple, O pink, C gray, H light blue.
Figure 3. Perspective views of the Ln4(OH)4 clusters in a) 3Gd, b) 3Tb,
c) 3Dy, d) 3Ho, e) 3Er, f) 3Tm, g) and 3Yb.
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disordered aqua species, without forming {Ln4(OH)4}8+ cu-
imental evidence of a magnetic cooling effect due to {Gd4-
bane clusters. Note that the direct reactions of Ln(OAc)3 and
K6[1] in aqueous media resulted in the precipitation of
amorphous solids containing Ln3+ and [1]6À in a 2:1 ratio. This
result indicates that the interstitial spaces in the hydrogen-
bonding framework act as a template available for creating
lanthanide clusters. Such a template effect due to interstitial
spaces has not been reported in discrete supramolecular
systems to date.
(OH)4}8+ cubane.
Catalytic Activities of 3Ln
Catalytic hydrolysis is one of the most attractive applica-
tions of lanthanide clusters.[29] Nevertheless, reports on the
heterogeneous catalytic activity of lanthanide clusters are
very rare.[30] We examined the catalytic hydrolysis of a phos-
phate ester as a representative example of Lewis acid
catalysis. The crystals of 3Ln (3.0 mg) were soaked in an
aqueous buffer solution (100 mm, pH 8.3) containing p-nitro-
phenyl phosphate (p-NPP, 25 mm) as the substrate (Support-
ing Information, Figure S15a). During the reaction, p-NPP
was decomposed into p-nitrophenolate (p-NP) and phosphate
by the hydrolysis reaction, which was monitored by a UV/Vis
Magnetic Properties of 3Ln
To determine whether magnetic interactions exist be-
tween the Ln3+ centers in the {Ln4(OH)4}8+ cubane, temper-
ature-dependent magnetic susceptibility measurements (H =
1000 Oe, T= 2–300 K) were performed for 3Ln (Figure 4a). At
300 K, these compounds gave cMT values (cm3 KmolÀ1) of 30.5
(3Gd), 44.1 (3Tb), 49.7 (3Dy), 53.0 (3Ho), 41.6 (3Er), 21.7 (3Tm),
and 9.58 (3Yb), which are similar to the expected values for the
four isolated Ln3+ ions (31.5 for GdIII4, 47.2 for TbIII4, 56.4 for
DyIII4, 56.2 for HoIII4, 45.9 for ErIII4, 28.6 for TmIII4, and 10.3
for YbIII4).[26] The magnetic features of these compounds are
consistent with previous reports that show the absence of
magnetic interaction between Ln3+ centers in cubane-type
lanthanide clusters.[15,27] We also investigated the molar
spectrophotometer
(Supporting
Information,
Fig-
ure S15b).[19,31] As illustrated in Figure 4b, the catalytic
activities of 3Ln vary depending on the type of Ln3+ in the
compound. It is common that the activities increase going
from Gd3+ to Lu3+, as their Lewis acidities increase owing to
the contraction of the ionic radii.[16] This is also the case for
the present system from 3Gd to 3Er. However, the activities
decrease from 3Er to 3Lu, with 3Lu showing the lowest activity
in this system. It is assumed that large lanthanide ions can
expand the gate of the framework to a greater extent, which
allows the substance to approach the catalytic Ln3+ centers
inside the crystal more easily. Thus, the unusual trend in the
catalytic activities of 3Ln results from the balance between the
gate sizes of the framework and the Lewis acidities of the Ln3+
ions. This is the first report that shows the heterogeneous
catalytic activities of a series of lanthanide-cubane clusters
installed in MOFs.
magnetocaloric effects owing to lanthanide ions using 3Gd
,
considering that the Gd3+ has the largest spin value (7/2)
among lanthanide ions.[16,26] The ÀDSm
value for 3Gd was
max
evaluated to be 46 JKÀ1 molÀ1 (Supporting Information,
Figure S13).[19] This value is comparable with that reported
for [Gd4(OH)4(C2O4)(H2O)5(SO4)3] having a {Gd4(OH)4}8+
cubane core (60 JKÀ1 molÀ1).[28] With this result in hand, we
subjected a pelletized sample (1.1 mg) of 3Gd to an external
magnetic field of 5T at 2.6 K to investigate the magnetic
cooling ability of 3Gd. When the magnetic field was reduced
from 5T to 2T, drastic cooling from 2.6 K to 1.8 K was Conclusion
observed (Supporting Information, Figure S14). Further cool-
ing was not observed even when the magnetic field was
reduced from 2T to 0T. On the other hand, increasing the
magnetic field from 0T to 3T resulted in the temperature of
the sample increasing by 0.6 K. Thus, 3Gd can be used as
a magnetic cooling material that can cool below 2 K under
magnetic fields of 2–5T. Note that this is the first exper-
We found in this study that the K+ ions in K6[1] are easily
completely exchanged by Ln3+ ions in the SCSC manner when
soaking its crystals in aqueous ethanol containing Ln(OAc)3.
Of note is the formation of hydroxide-bridged lanthanide
cubanes that connect [1]6À anions in the 3D MOF structure.
The formation of these cubanes was dependent on the size of
the Ln3+ ions; the MOF structure in 3Ln was formed for later
lanthanides (Gd3+, Tb3+, Dy3+, Er3+, Ho3+, Tm3+, Yb3+, and
Lu3+), whereas early lanthanide ions (La3+, Ce3+, Pr3+, Nd3+,
Sm3+, Eu3+) gave ionic solid structures in 2Ln. Thus, a series of
lanthanide cubanes (Ln = Gd–Lu) with the same structure
and coordination environment were created for the first time
via a simple, straightforward postsynthetic modification
approach. This enabled us to perform systematic investiga-
tions of the magnetic and catalytic properties of the lantha-
nide cubanes installed in MOF structures, demonstrating their
potential applications as magnetic cooling materials and
heterogeneous catalysts. Considering that the interstitial
spaces surrounded by free carboxylate groups of [1]6À
function as templates for creating the lanthanide cubane
clusters, the development of other ionic crystals of coordina-
Figure 4. a) The cMT versus T plots of 3Ln (H=1000 Oe). b) The
catalytic hydrolysis of p-nitrophenyl phosphate (p-NPP) by 3Ln under
heterogeneous conditions.
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Acknowledgements
This work was supported by JST CREST (Grant No.
JPMJCR13L3) and JSPS KAKENHI (Grant Nos. 19K05496
and 18H05344). The synchrotron radiation experiments were
performed at Spring-8 with the approval of JASRI (Proposal
Nos. 2019A1279, 2019A1302, 2019B1107, and 2019B1108)
and at 2D-SMC of the Pohang Accelerator Laboratory.
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Conflict of interest
The authors declare no conflict of interest.
Keywords: cluster compounds · crystal engineering ·
lanthanides · postsynthetic modification
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Angewandte
Research Articles
Chemie
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Manuscript received: June 11, 2020
Version of record online: && &&
,
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Angew. Chem. Int. Ed. 2020, 59, 2 – 8
ꢀ 2020 Wiley-VCH GmbH
www.angewandte.org
&&&&
These are not the final page numbers!

Angewandte
Research Articles
Chemie
Research Articles
Lanthanides
Soaking crystals of K6[Rh4Zn4O(l-cystei-
nate)12] in a lanthanide acetate solution
results in the complete exchange of K+
with Ln3+ in a single-crystal-to-single-
crystal process. For late lanthanides (Ln=
Gd–Lu), this process afforded a series of
lanthanide cubane clusters with a [Lu4(m3-
N. Yoshinari, N. Meundaeng, H. Tabe,
Y. Yamada, S. Yamashita, Y. Nakazawa,
T. Konno*
&&&& — &&&&
Single-Crystal-to-Single-Crystal
Installation of Ln4(OH)4 Cubanes in an
Anionic Metallosupramolecular
Framework
OH)4]8+ core, which connect the RhIII4ZnII
4
complex anions in a 3D MOF structure,
showing magnetic cooling and heteroge-
neous catalytic abilities.
&&&&
www.angewandte.org
ꢀ 2020 Wiley-VCH GmbH
Angew. Chem. Int. Ed. 2020, 59, 2 – 8
These are not the final page numbers!