Cage-like crystal packing through metallocavitands within a cobalt cluster-based supramolecular assembly

Article abstract of DOI:10.1039/c8dt00747k

A cobalt (Co) supramolecular triple-stranded helicate, [Co₈(PDA)₆(Br-PTA)₃(DMF)₄(H₂O)₂] (1) (PDA = 2,6-pyridinedicarboxylate, Br-PTA = 5-bromoisophthalate, DMF = dimethylformamide), is succ

Full text of DOI:10.1039/c8dt00747k

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PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
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Cage-like Crystal Packing through Metallocavitands within a
Cobalt Cluster-based Supramolecular Assembly
Received 00th January 20xx,
Accepted 00th January 20xx
Philjae Kang, Hien Duy Mai, and Hyojong Yoo*
DOI: 10.1039/x0xx00000x
www.rsc.org/
A
cobalt (Co) supramolecular triple-stranded helicate,
The ‘cavitand’ was introduced for synthetic organic
[Co8(PDA)6(Br-PTA)3(DMF)4(H2O)2]
(1)
(PDA
=
2,6- compounds that possess cavities to enclose other molecules
and ions via host-guest interactions.11-14 The representative
pyridinedicarboxylate, Br-PTA
=
5-bromoisophthalate, DMF
=
dimethylformamide), is successfully synthesized and fully examples of organic cavitand scaffolds include calixarenes,15, 16
characterized. The solid-state structure of 1 shows that four cobalt resorcinarenes,17,
cyclotriveratrylenes,19 cucurbiturils,
24
Recently, it was found that the
18
20-22
atoms are coordinated by three PDA ligands to form
a
and cyclodextrins.23,
tetranuclear cobalt cluster with three extension points and the transition metals of the metallocavitands play a vital role in the
ditopic Br-PTA ligands interlink two basic assembly units. In crystal formation of cavities and inclusion properties. Most of those
packing, the bromo group is surrounded by the cavity-like examples reported to date show intermolecular interactions
tetranuclear cobalt cluster, which acts as a metallocavitand, to between the multimetallic clusters acting as cavities and guest
generate
a
unique cage-like crystal packing geometry. The molecules or groups.25-29
Interestingly, the host-guest
isomorphous molecular cage, which exhibits similar crystal- properties of the metallocavitands can strongly affect the
packing geometry as observed in 1, is also successfully isolated. formation of crystal packing geometries in the solid-state
This is an unusual example of a highly symmetric cage-like crystal structures.30, 31 Moreover, as a single metallosupramolecule
packing architecture, resulting from the interaction among possesses both the cavity as a host and the functional groups
metallocavitands of in-situ generated supramolecular modules.
as a guest, the host-guest interactions between molecules
could lead to the connections of supramolecular modules and
generate another level of solid-state metallosupramolecular
assemblies with a high degree of symmetry and intricacy.
More importantly, distinctive chemical and physical properties
induced from the higher-ordered structure can be observed.9,
32 This is a unique synthetic strategy to prepare new solid-state
materials.
Introduction
The coordination-driven metallosupramolecular platforms with
multinuclear metal clusters and various di- or multitopic
organic ligands have been extensively investigated in recent
years.1-4 In most cases, the structural diversity, symmetry, and
complexity of targeted supramolecular or polymeric
architectures arise from the use of simple coordination modes
involving the assemblies of two or more metal ions
coordinated by multitopic ligands or a multilevel assembly of
multinuclear metal clusters.5-7 Additionally, more advanced
assembly modes can be used to produce discrete molecular
platforms or coordination polymers with structural hierarchy.8-
Herein, we report an approach to metallosupramolecular
crystal packing platforms featuring a structural hierarchy. Two
cobalt cluster-based assembly units are interlinked by ditopic
ligands to form a cobalt supramolecular triple-stranded
helicate, [Co8(PDA)6(Br-PTA)3(DMF)4(H2O)2] (1), wherein the
bromo group is surrounded by the tetranuclear cobalt cluster
metallocavitand to generate a unique cage-like assembled
10
crystal structure. Two molecular cages (
2 and 3) with similar
The unique structural and physical properties in these
crystal-packing geometry to 1 are successfully isolated in the
assemblies can be tailored by the rational design of
supramolecular modules and molecular interactions.9
separate reaction. The solid-state structures and synthetic
strategies of these assemblies are discussed.
Results and Discussion
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Treatment of 1 equiv. of Co(NO3)2·6H2O, 2 equiv. of 2,6- (e.g., lower symmetries of P21/n or P3121).8, 10 The solid-state
pyridinedicarboxylic acid (H2PDA), and equiv. of 5- structure of shows that a tetranuclear cobalt cluster is
bromoisophthalic acid (Br-PTA) in DMF at 100 C for 6 h leads formed through a coordination-driven assembly of four cobalt
to the formation of [Co8(PDA)6(Br-PTA)3(DMF)4(H2O)2] (
(PDA 2,6-pyridinedicarboxylate, Br-PTA
bromoisophthalate, DMF
Complex is isolated as purple rectangular crystals (30.5 % adopts pseudo-octahedral geometry, is surrounded by six
yield based on the amount of H2PDA used). The solid-state oxygens from three PDAs and three Br-PTAs (Figure S1a). The
structure of is determined by single crystal X-ray diffraction remaining three surrounding Co atoms (Co2–Co4) also show
1
1
º
1) ‡ (Co) atoms and three PDAs (Figures 1a and 1b). The resulting
=
=
5- tetranuclear cobalt cluster acts as a basic unit with three
=
dimethylformamide, Eq. 1). extension points. Specifically, the central Co atom (Co1), which
1
1
(XRD) analysis, and the structure is solved and refined as the pseudo-octahedral geometry; each is bound to one nitrogen
space group Fd-3 with a unit cell volume of approx. 208560 Å3 and two oxygens from a tridentate PDA, one oxygen from an
(Figure 1 and Table S1). Such a high packing symmetry and adjacent PDA, one oxygen from a Br-PTA, and one oxygen from
large unit cell volume of
1 have never been observed in other a solvent molecule (i.e., H2O or DMF) (Figure S1b). In addition,
previously reported supramolecules with helical structures one of the carboxylate groups from the tridentate PDA ligand
forms a μ-carboxylato bridge between the central and terminal
Co atoms. Notably, the orientation of the terminal Co-PDA
coordination spheres resembles a trigonal pyramid defined by
Co1 at an apex and three oxygens (O12, O21, and O33) at the
corners, generating a cone-shaped cavity possessing C3
symmetry (Figures 1a and 1b). The distances between the
central and surrounding Co atoms are in the range of 3.49–
3.54 Å, and those between surrounding Co atoms varies from
5.60 to 5.68 Å. As mentioned before, this tetranuclear cobalt
clusters can be assigned as a metallocavitand, in which
multimetallic metal-ligand coordination modes are critical for
the cavity formation. The metallocavitand tetranuclear cobalt
clusters are diagonally interlinked by ditopic Br-PTAs to form a
cobalt supramolecular triple-stranded helicate (TSH, 1), which
shows rotation symmetry through the C2 axis passing between
the two cobalt clusters. The separation between the two
central Co atoms (Co1···Co1) is ~7.22 Å and the bromo groups
in
1 are directed away from the center of the TSH (Figure S2).
This orientation likely minimizes the steric hindrance between
the bromo groups.
The temperature-dependent magnetization (cm3/g)
measurements of
MPMS-5XL magnetometer for temperatures 3 K ≤
with an applied field of 1000 Oe. The fitting of the 1/
1
are performed using a Quantum Design
≤ 300 K
vs
ꢀ
ꢁ
ꢀ
curve (Figure S3a) yields a value of ꢂ ꢃ –12.1 K, which suggests
an antiferromagnetic interaction between the cobalt ions.33, 34
The value of ꢁꢄꢀ at 300 K is ~3.04 cm3 K mol–1 (Figure S3b).
This value, while higher than the estimated spin-only value of
1.88 cm3 K mol–1 for
ꢅ = 3/2, still falls within an acceptable
range for high-spin octahedral Co(II) ions.8, 35-38 This result is
further confirmed by calculating the bond valence sums using
the observed bond distances in the crystal structure data
Figure 1. X-ray crystal structure of 1 and the simplified cartoons illustrating the
structural assembly in 1. Complex 1 is composed of two tetranuclear cobalt clusters (a
and b, portrayed in buckets) interconnected by two Br-PTAs to form a TSH (c). All the
coordinated and free solvent molecules, and hydrogen atoms have been omitted for
clarity. Colors: C gray, N blue, O red, Co yellow, and Br green.
(Table S4).39, 40 Given the oxidation state of Co(II),
1 would bear
a charge of -2. On this basis, there should be counter ions to
neutralize the net charge of these complexes. Although the
2 | J. Name., 2012, 00, 1-3
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Figure 3. Molecular cage 2 composed of six TSHs (portrayed in different colors) as
monomers, which are bridged by four Co5 atoms (yellow spheres). Insets: (top) Crystal
structure of a TSH generated in situ and (bottom) coordination mode of a bridging Co5
atom. All the coordinated and free solvent molecules, hydrogen atoms, and disorder
components of bromo groups have been omitted for clarity. Color of atoms for the
insets: C, grey; N, blue; O, red; Co, yellow; Br, green.
experimental and simulated PXRD patterns. The
thermogravimetric analysis (TGA) (Figure S5) of
minor weight loss before 350 C, attributed to the removal of
coordinated DMF and H2O molecules. After 400 C, the
occurs, which indicates its excellent
1 shows a
º
º
decomposition of
thermal stability.
1
The crystal packing of 1 in the solid state can be considered
to be a result of the host-guest interactions among
metallocavitands, which occur collectively between
neighboring TSHs. The cone-shaped cavity provides sufficient
space to the bromo group in Br-PTA to lead to a close packing.
It is assumed that the inner space of cone-shaped cavity of
1
could be electron deficient because of the presence of four
Co2+ ions in the cluster. A similar electron deficiency in
multinuclear metal clusters and their binding capability to
guests were also reported previously.43 The bromine atoms,
which are highly electronegative, could be located near.of the
neighboring supramolecule in solid state packing (Figures 2a
and S6). The shortest Br···C7 distance in
Å, which is slightly longer than the summated values of the van
der Waals radii of Br and C (3.55 Å).44 The complex
, as a
1 is found to be 3.63
1
Figure 2. (a) Cartoons illustrating the interactions between the coned-shaped cavity
and the bromo group in Br-PTA; (b) Crystal packing in the connection of one TSH to
other four TSHs; (c) Cage-like crystal packing of six TSHs; (d) The packing of
neighboring cage-like structures of 1 in solid state. Green spheres refer to the bromine
atoms. The cage-like structures of 1 in (d) are portrayed in different color for clarity.
Inset in (d) reveals the interactions among metallocavitands of neighboring cage-like
structures of 1.
metallocavitand, possesses both the cavity as a host and the
functional groups as a guest within a single molecule. The two
bromo groups in a single TSH are located within the cavities of
two other TSHs and another bromo group is oriented toward
the center of the packing assemblies. Consequently, this leads
to the connection of one TSH to four other TSHs (Figure 2b). In
a different view, six TSHs are arranged circularly in a cage-like
crystal packing, in which the six bromo groups form an
octahedral arrangement with the Br···Br distances of 8.67 Å
and 12.26 Å (Figures 2c and S7). In this packing geometry, TSHs
are not chemically connected, but circularly arranged in a
highly symmetric and well-organized cage-like packing,
primarily as a result of the host-guest interaction among
location of the counter ions could not be precisely found using
single crystal XRD analysis due to the severe disorder of
uncoordinated solvent molecules (DMF), we speculate that the
net charge of
1 can be balanced by the incomplete
deprotonation of ligands or by dimethylammonium
counterions formed through the decarbonylation of DMF at
42
The phase purity of the as-
elevated temperatures.41,
synthesized TSH
1 is confirmed by powder XRD (PXRD) (Figure
metallocavitands. In solid state, the packing of
1 can be also
S4). The data show considerable similarities between the
designated as the arrangement of cage-like structures (Figure
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Figure 5. Adsorption isotherms of 1, 2, and 3 for CO2 and N2 at 273 K.
unoccupied carboxylate oxygens to form a highly symmetric
molecular cage of . It is interesting to note that the
aforementioned cage-like packing of is almost identical to
the cage structure of , except for the packing of having no
(Figures S7
, the use of
2
Figure 4. Molecular cage 3 with I-PTAs. Purple and yellow spheres represent iodine
1
and cobalt atoms, respectively.
2
1
connecting cobalt ions as observed in the case of
and S8). In the synthesis of the molecular cage
2
2d) with interactions among metallocavitands. Although the
TSHs in the previous studies also comprise geometrically
similar tetranuclear cobalt clusters, the lack of an
electronegative group on the 3-position on the benzene ring of
the substituted PTA ligands (i.e., isophthalate and 5-tert-
butylisophthalate) would be the reason for their different and
2
excess Co precursor may lead to the formation of the
interconnecting cobalt sites in between monomeric TSHs. In
fact, in the presence of excess amount of Co ion, a similar
complex packed with the Fd-3 space group was obtained using
5-tert-butylisophtalate.8
lower crystal-packing symmetries compared to 1. In addition,
To clarify the importance of halides in TSH for the
interaction among metallocavitands, 5-iodoisophthalic acid (I-
PTA) is synthesized and utilized for the assembly.45 Treatment
of an excess (more than 3 equiv.) of Co(NO3)2·6H2O, 2 equiv. of
H2PDA, and 1 equiv. of H2I-PTA in DMF affords {[Co8(PDA)6(I-
in their respective crystal packing geometries, we have never
observed any contacts such as intermolecular host-guest
interactions in their solid state structures. On this basis, we
consider that bromine atoms and the corresponding host-
guest interaction among metallocavitands would play an
PTA)3(DMF)4(H2O)2]6-[Co(H2O)3]4} (
the amount of H2PDA used). The solid-state structure of
(Figure 4) is determined by the single-crystal XRD method and
shows that is another molecular cage composed of six TSHs
with I-PTAs. The basic structure of is isomorphous with
except for the presence of iodo groups. The chemical states of
the Co species in and are investigated using temperature-
dependent magnetization (Figure S9) and bond valence sum
analysis (Table S4). It is found that all cobalt species in and
are in the +2 oxidation states. The experimental PXRD patterns
of the microcrystals of and are consistent with their
respective simulated data, revealing the purity and collective
formation of and (Figures S10 and S11, respectively).
Thermal stability investigated by TGA shows that the
decomposition of and occurs at around 380 C (Figure S12).
As there are considerable similarities in the crystal packing
and , only the crystal packing of the former has been
3) (49.9 % yield based on
important role to govern the cage-like crystal packing of
1.
3
The molecular cage 2, which has very similar geometry to
the cage-like packing shown in Figure 2c, is successfully
isolated in separate reactions. For example, the reaction of an
excess (more than 3 equiv.) of Co(NO3)2·6H2O, 2 equiv. of
3
3
2,
H2PDA, and
{[Co8(PDA)6(Br-PTA)3(DMF)6]6-[Co(H2O)3]4} (
based on the amount of H2PDA used). Single-crystal XRD
analysis of reveals that it crystalizes in a cubic (Fd-3 space
group) system (Table S2), which is similar to that of
that the unit cell volume of is smaller than that of
Å3. The solid-state structure of
1
equiv. of H2Br-PTA in DMF affords
2
3
2) (41.4 % yield
2
3
2
1, except
2
3
2
1 by 9716
2
(Figure 3), analyzed by single-
crystal XRD, shows that it is composed of six TSHs. Although
the coordinated solvents in (four DMF and two H2O
molecules) are different from those in the monomeric TSH (six
DMF molecules) in , both structures and are geometrically
2
3
1
2
3
º
2
1
2
of
2
3
similar as they are constructed from the assembly of two
tetranuclear cobalt clusters with similar orientation of Br-PTA
ligands. In particular, the monomeric TSHs (inset in Figure 3)
are interconnected by four pseudo-octahedral Co5 sites via its
examined in detail and demonstrated as a representative for
both types of molecular cages (Figure S13). Specifically, the
interactions among metallocavitands between two adjacent
molecular cages of
2 (coded in different colors for sake of
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clarity) are similarly observed in the crystal packing of
1
; i.e., different isomorphous molecular cages (
2
and
3
), which exhibit
, are also
tetranuclear cobalt clusters (serving as a cone-shaped cavity) similar crystal-packing geometry as observed in
1
from one cage could accommodate the bromo groups from successfully isolated from separate reaction. These are unusual
the neighboring cage (Figure S13a). In addition, each central examples of a highly symmetric crystal packing architecture,
cage is exposed to four neighboring ones (Figure S13b). The resulting
shortest distance between bromine atoms and C7 in is 3.63 metallocavitands of in-situ generated supramolecular
Å. On the other hand, the shortest distance between iodine modules.
atoms and C11 in is 3.74 Å, which demonstrates the larger This research was supported by the National Research
from
the host-guest interaction
within
2
3
guest is being interacted. The halide groups such as bromo and Foundation of Korea (NRF) grant funded by the
iodo groups are presumably critical to form the cage-like Korea government (MSIP) (NRF-2015R1A4A1041631 and NRF-
crystal packings in the assemblies of cobalt-cluster based 2016R1A2B4009281). This research was supported by Hallym
suplamolecules (TSH).
The highly symmetric cage structures and cage-like crystal Experiments at PLS-II were supported in part by MSIP and
packing through the metallocavitands in , and is POSTECH (2017-3rd-2D-017). Magnetic measurements were
beneficial for gas adsorption. Therefore, the gas capture performed using facilities at IBS Center for Correlated Electron
performances of metallocavitands are examined. Prior to Systems, Seoul National University.
University Research Fund, 2017 (HRF-201709-010).
1,
2
3
1-3
the gas adsorption experiments, the solvent molecules in the
samples are removed by successive acetone exchanges and
dried under vacuum for 36 h. The CO2 adsorption
Conflicts of interest
measurements at 273 K (Figure 5) show an uptake of 11.4 cm3
There are no conflicts to declare.
1
g− for
(25.3 cm3 g− ) and
1, which is somewhat less than that achieved with
1
2
1
3
(20.1 cm3 g− ). In particular, the three
compounds show very little N2 adsorption properties at 273 K,
which is attributed to a more favoured interaction between
CO2 and the exposed metal sites in comparison with N2 (Figure
Notes and references
‡ The formula, [Co8(PDA)6(Br-PTA)3(DMF)4(H2O)2], is proposed
based on the crystallographic structure of 1 obtained from SCXRD
analysis, which does not show any counter ions.
5).46-48 The higher CO2 uptakes in
2 and 3 as compared to 1 is
presumably because of the presence of extra metal sites, i.e.,
Co5. The Co5 sites, while serving as connecting sites, are
bound to the H2O ligands, which can be readily removed by
the desolvation step. This results in more exposed metal sites
that could induce better interactions with a higher quadrupole
moment and polarizability of CO2.46 In the previous study,8 we
found that a similar cage structure showed markedly higher
CO2 adsorption capacity than did the monomer TSH. One of
the possible reason for the gas adsorption enhancement of the
tbu-cage could be the presence of linking cobalt atoms that
favoring the interaction with CO2 molecules. However, we
could not provide any experimental evidences for it in the
previous report. In the current work, since the only difference
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DOI: 10.1039/C8DT00747K
Table of Content for
Cage-like Crystal Packings through Metallocavitands within Cobalt Cluster-
based Supramolecular Assembly
The generation of cage-like crystal packing geometry of TSHs in the solid state induced by the host-guest interactions
among metallocavitands.