An Exceptionally Stable Metal-Organic Framework Constructed from Chelate-Based Metal-Organic Polyhedra

Article abstract of DOI:10.1021/jacs.0c01626

We report the rational design and synthesis of a water-stable metal-organic framework (MOF), Fe-HAF-1, constructed from supramolecular, Fe³⁺-hydroxamate-based polyhedra with mononuclear metal nodes. Owing to its chelate-based construction, Fe-H

Full text of DOI:10.1021/jacs.0c01626

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An Exceptionally Stable Metal-Organic Framework
Constructed from Chelate-based Metal-Organic Polyhedra
Jerika A. Chiong, Jie Zhu, Jake B Bailey, Mark Kalaj, Rohit
Subramanian, Wenqian Xu, Seth M. Cohen, and F. Akif Tezcan
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c01626 • Publication Date (Web): 28 Mar 2020
Downloaded from pubs.acs.org on March 28, 2020
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An Exceptionally Stable Metal-Organic Framework
Constructed from Chelate-based Metal-Organic Polyhedra
Jerika A. Chiong,1,‡ Jie Zhu,1,‡ Jake B. Bailey,1,‡ Mark Kalaj,1 Rohit H. Subramanian,1 Wenqian Xu2,
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Seth M. Cohen,1 and F. Akif Tezcan1,3,*
1Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093
2X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, IL 60439
3Materials Science and Engineering, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093
Supporting Information Placeholder
range of metals.26 These functional groups are found in
ABSTRACT: We report the rational design and synthesis of a
siderophores, which are small organic molecules produced by
bacteria to scavenge metal ions, most notably Fe3+, with
remarkable affinities.27-28 Hydroxamates are an attractive
chelating group for the synthesis of extended structures since they
are rotationally flexible and sterically unencumbered with a
coordination footprint similar to commonly used carboxylates.
water-stable metal-organic framework (MOF), Fe-HAF-1,
constructed from supramolecular, Fe3+-hydroxamate-based
polyhedra with mononuclear metal nodes. Owing to its chelate-
based construction, Fe-HAF-1 displays exceptional chemical
stability in organic and aqueous solvents over a wide pH range
(pH 1-14), including in the presence of 5 M NaOH. Despite the
charge-neutrality of the Fe3+-tris(hydroxamate) centers, Fe-HAF-1
crystals are negatively charged above pH 4. This unexpected
property is attributed to the formation of defects during
crystallization that results in uncoordinated hydroxamate ligands
or hydroxide-coordinated Fe centers. The anionic nature of Fe-
HAF-1 crystals enables selective adsorption of positively charged
ions in aqueous solution, resulting in efficient separation of
organic dyes and other charged species in a size-selective fashion.
Fe-HAF-1 presents a new addition to a small group of chelate-
A previous example of a hydroxamate-containing MOF was
reported by Farha and Hupp, whereby 1,4-benzenedihydroxamic
acid (p-H2bdh) was incorporated into a Zr-based MOF (UiO-66)
via postsynthetic exchange,29 with the resulting framework stable
under alkaline conditions. Recently, Martí-Gastaldo reported a Ti-
p-H2bdh-based MOF, MUV-11, prepared by direct synthesis.30
However, the hydroxamate-mediated connectivity of this
framework only extended in two dimensions. Indeed, most MOFs
containing chelating motifs, such as those based on catechol
groups, form either 2D sheets connected by noncovalent
interactions (π-π stacking or H-bonding) or employ monodentate
ligands to facilitate connectivity in the third dimension.31-34 A rare
exception was provided by protein-MOFs in which p-H2bdh
linkers were employed to link spherical ferritin molecules into
porous, crystalline 3D lattices.35-36 In comparison to extended 3D
frameworks, chelate-based ligands are more prevalent in metal-
organic polyhedra (MOPs).37-39 In fact, MOPs have been
previously used as building blocks (or SBUs) for construction of
MOFs with diverse structures and properties.40 In this work, we
employed this strategy to generate the first example of a 3D Fe-
hydroxamate framework, namely Fe-HAF-1. Inspiration for the
based MOFs and provides
a rare framework whose 3D
connectivity is exclusively formed by metal-hydroxamate
coordination.
Metal-organic frameworks (MOFs) are a class of porous,
crystalline materials1-3 with many potential applications in
catalysis,4-9 gas storage,10-11 drug delivery,12-13 molecular
separation,14-17 and molecular sensing.18-19 MOFs are comprised
of metal nodes and bridging organic ligands that form highly
ordered structures.20-21 Each node is comprised commonly of
polynuclear clusters of metal atoms, also known as secondary
building units (SBUs). The introduction of the SBU concept has
allowed access to diverse node geometries, ultimately leading to
MOFs with greater structural complexity.22 Early SBUs were
primarily composed of divalent transition metals (Zn2+ or Cu2+)
and carboxylate groups.23-24 The metal-ligand bonds in these
nodes are relatively weak and prone to hydrolysis in aqueous
conditions.1 Infiltration of water molecules into the SBUs of these
MOFs undermines the structural integrity of the materials,
eventually leading to collapse of the crystalline framework. One
successful approach to improve the aqueous stability of the
framework is to selectively design nodes with stronger metal-
ligand bonds.25
chelate-based SBU was derived from
a tetrahedral M4L6
coordination cluster reported by Raymond.39 This cluster was
based on the isophthal-di-N-(4-methylphenyl)hydroxamic acid as
the linker and Fe3+/Ga3+ as the metal node, with four
dimethylformamide (DMF) molecules partially filling the rigid
cavity. This design successfully demonstrated that a combination
of a three-fold symmetry at a pseudo-octahedral metal center with
a rigid linker containing two-fold symmetry can create a
symmetry-driven tetrahedral cluster.39
We prepared a nearly identical cluster by combining m-
benzenedihydroxamic acid (m-H2bdh) and FeCl3 in DMF at room
temperature (Figure 1). m-H2bdh lacks the N-toluyl groups used in
the previously reported ligand,39 forming the desired cluster with
reduced steric bulk. Fe4(m-bdh)6 clusters crystallized readily into
Chelating ligands, such as catecholates and hydroxamates, are
well known for their ability to form strong bonds with a wide
a
lattice with P213 symmetry. As expected, each Fe-
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tris(hydroxamate) center formed a C3 vertex of the discrete
calculated accessible surface area of 2160 m2/g, the N2 adsorption
isotherm at 77 K for the Fe-HAF-1 revealed no significant gas
uptake (BET <10 m2 g-1); similar results were reported with a 3D
Fe-catecholate framework (Fe-CAT-5).34 We ascribe the low N2
adsorption uptake to DEF molecules retained in the pores as well
as within the individual tetrahedral SBUs (Figure S12).
Conventional activation protocols led to the structural collapse of
Fe-HAF-1 upon evacuation of solvent molecules (SI Methods).
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cluster. Because each metal center is chiral, each discrete cluster
can have T (∆∆∆∆ or ΛΛΛΛ), C3 (∆∆∆Λ or ΛΛΛ∆), or S4
(∆∆ΛΛ) symmetry in solution. Each unit cell is comprised of
eight clusters with T symmetry (four ∆∆∆∆ and four ΛΛΛΛ). On
average, the Fe-carbonyl and Fe-hydroxyl bond lengths are 2.05 Å
and 1.98 Å, respectively. The clusters in this crystal lattice are
held together by a series of H-bonding and π-π stacking
interactions (Figure S3). Each cluster has an interior cavity that is
ca. 7.5 Å in diameter (Figure 1).
The ability of MOFs to resist degradation under harsh chemical
conditions is directly linked to the strength of the metal-ligand
bonds at their nodes.25 In particular, hard, carboxylate-based
linkers are known to give rise to a wide variety of stable
frameworks43 with hard, high-valent metal ions, including MIL-53
(Cr3+), MIL-100 (Fe3+), and UiO-66 (Zr4+).44-46 Accordingly, we
expected that Fe-HAF-1 would also exhibit high chemical
stability, which could be further bolstered by the chelating nature
of the hydroxamate ligands. As shown in Figure 3a, Fe-HAF-1
retained its crystallinity under both highly acidic (pH 1) and
highly basic conditions (5 M NaOH), which compares favorably
to the very stable carboxylate-based MOFs, such as UiO-66
(Figure S10)47 and the highly alkaline-stable frameworks, ZIF-8,
PCN-601, and ZrPP-1.48 In addition to providing excellent
aqueous stability, the strong bonds of the chelate-based node also
resist decomposition across a range of coordinating solvents, such
as carboxylic acids and amines as well as other common organic
solvents (Figure 3b). To further confirm the structural integrity of
the frameworks, we analyzed the samples by scanning electron
microscopy (SEM) after incubation under different conditions.
SEM images indicated that Fe-HAF-1 maintained its cubic
morphology in all cases (Figure S11). Our findings illustrate that
it is possible to attain very high chemical stability in a porous
framework even with mononuclear metal nodes.
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Figure 1. Ball-and-stick representation of a single discrete cluster
of ∆-Fe4(m-bdh)6. The blue sphere highlights the central cavity of
the cluster. Gray, red, blue, white, and orange spheres represent C,
O, N, H, and Fe atoms, respectively.
To connect Fe4(m-bdh)6 clusters into an extended 3D
framework (Fe-HAF-1), we synthesized a linear dimer of m-
H2bdh, biphenyl tetrahydroxamic acid (H4BPTH) (Figure 2a).
Reaction of the H4BPTH linker with FeCl3 in a solution of N,N-
diethylformamide (DEF) and 1,4-dioxane at 70 °C for 24 h
yielded a dark-red microcrystalline powder of Fe-HAF-1, which
consisted of 4-6 µm cube-shaped particles (Figure S4). Powder X-
ray diffraction (PXRD) measurements indicated a face-centered
cubic lattice with a = 34.566 Å (Figure 2b). Through slow
temperature-ramping and -cooling steps during synthesis, we
obtained ca. 100-μm-sized crystals that were suitable for single-
crystal X-ray diffraction (sc-XRD). Much like the
microcrystalline powder, these crystals all exhibit a cubic
morphology (Figure S5) with a chiral lattice (F432), in which
each tetrahedral, hydroxamate-based SBU is connected to six
adjacent SBUs through the bridging ligand. The pores that form
between individual clusters are approximately 16 Å in diameter
(Figure 2c), with 8 Å apertures. Each cluster maintains a cavity
with a 7.5 Å diameter. The topology of Fe-HAF-1 is twisted
boracite (tbo), with the underlying net consisting of C3 vertices at
each metal and C4 vertices at each ligand, yielding a similar lattice
architecture as the canonical Cu-based MOF, HKUST-1.41 The
phenyl-phenyl dihedral angle is 20.4°, which is similar to other
MOFs (such as UiO-67) containing biphenyl bridging ligands.42
Unlike the discrete Fe4(m-bdh)6 cluster, which possesses T, C3, or
S4 symmetry in solution and exists as a racemic mixture of ∆ and
Λ in the crystal lattice, the linker connectivity in Fe-HAF-1 leads
to enantiopure (either ∆ or Λ) crystals. Because there is no
preference for either ∆ or Λ during MOF synthesis, the bulk
sample exists as a racemic mixture.
Figure 2. (a) The chemical structure of H4BPTH. (b) PXRD
pattern for Fe-HAF-1 is consistent with a face-centered cubic
lattice. (c) The unit cell of the Fe-HAF-1. The internal pore is
highlighted by a yellow sphere (16 Å), and the cavity of the
cluster is highlighted with a blue sphere (7.5 Å). (d) A
representation of the 3D network of Fe-HAF-1.
Interestingly, despite an expected neutral charge based on its
composition, we observed that Fe-HAF-1 behaved as an ionic
MOF. Zeta potential measurements (Figure S7) indicated that Fe-
HAF-1 was highly negatively charged above a pH of 4. We
attribute this property to the formation of defects49 during
The thermal stability of Fe-HAF-1 was evaluated by
thermogravimetric analysis (TGA). The TGA curves displayed no
significant weight loss up to 120 °C (Figure S6). Despite the
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synthesis (owing to the highly chelating nature of the BPTH
3.8.51 Further implicating the formation of defects, FTIR spectra
of Fe-HAF-1 displayed O−H stretching vibrations as a broad peak
at 3180 cm-1 similar to the
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linker), which likely results in free hydroxamate groups or Fe3+
centers with hydroxide ligands.50 Notably, although the pKa of the
free hydroxamic acid is >8.5, polyhydroxamic acid polymers were
previously shown to display negative zeta potentials above pH
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Figure 3. PXRD patterns of Fe-HAF-1 after exposure to (a) aqueous solutions at different pH and (b) different organic solvents for one
week. All organic solvents were neat except for ammonium hydroxide (50% v/v). The simulated pattern was calculated using Λ-Fe-HAF-
1.
H4BPTH linker (Figure S8), consistent with the presence of free
hydroxamic acid groups.52 The possibility of mixed-valence Fe-
clusters (i.e., the presence of Fe2+ species), which could also give
rise to an overall negative charge, was ruled out by X-ray
photoelectron spectroscopy (XPS) measurements (Figure S9).53
test the recyclability of the MOF. In these experiments, LV+ was
first fully adsorbed into Fe-HAF-1 powders to obtain a colorless
solution, followed by a treatment with DEF or saturated NaNO3 to
induce the release of LV+ from the MOF. The results showed that
the uptake and release of the cationic dye were quantitative and
fully reversible over at least three cycles (Figure S22), whereby
the crystallinity of Fe-HAF-1 was largely preserved (Figure S21).
Ionic MOFs have been explored as platforms for selective
uptake of organic dyes.54-63 To evaluate the accessibility of
charged molecules to the pores of Fe-HAF-1, we chose four
cationic organic dyes (Methylene Blue (MLB+), Lauth’s Violet
(LV+), Rhodamine B (RB+), and Alcian Blue (AB4+)), a cationic
metal complex (Ru(bpy)32+), and two anionic organic dyes,
(Orange G (OG2-) and Rose Bengal (RB2-)) as potential guest
molecules. The size of all dyes except (AB4+) is suitable for pore
permeation (Figure S13). A typical sample used in uptake
measurements contained 5 mg of Fe-HAF-1 and initial dye
concentrations of 10 ppm, and the change in UV-vis absorbance
was monitored over time. As shown in Figures 4 and S14-19, the
cationic species (MLB+, LV+, RB+ and Ru(bpy)32+) were
efficiently taken up by Fe-HAF-1 over the course of 2-6 h, while
both anionic dyes (OG2- and RB2-) and the large cationic dye
AB4+ remained in solution. These results confirmed the anion-
and size-selectivity of Fe-HAF-1 for dye uptake. The selective
cation uptake by Fe-HAF-1 was further corroborated by
competition experiments using an equimolar (0.025 mmol)
mixture of the similarly sized by oppositely charged MLB+ and
OG2- dyes (Figure 4c), which showed that 97% of the former but
none of the latter was sequestered from solution over the course of
2 h. Similar competitive selectivity between cationic dye and
anionic dye was also observed with mixture of MLB+ and RB2-
(Figure S20).
In summary, we have rationally designed a new MOF, Fe-
HAF-1, which was constructed from tetrahedral, Fe3+-
hydroxamate-based clusters. This chelate-based, cubic MOF was
found to be not only stable in different organic solvents, but also
in water over a wide pH range (pH = 1 to 5 M NaOH), making it
one of the most alkaline-stable MOFs. High crystallinity could be
achieved despite the chelating nature of the tetra-hydroxamate
ligand H4BPTH, which led to the formation of defects during
crystallization and an attendant anionic character for Fe-HAF-1
MOFs. Consequently, Fe-HAF-1 crystals were highly selective
for the reversible uptake of positively charged dye molecules. Our
results, along with previous reports on protein-35-36 and Ti-based
MOFs,30 further establish hydroxamate functionalities as a
valuable addition to the synthetic toolkit for MOFs. In addition,
the large number of symmetry-driven coordination cages
described in the literature64-67 open up many opportunities for new
MOFs based on these supramolecular SBUs.
PXRD measurements indicated that Fe-HAF-1 remained
crystalline after dye uptake (Figure S21), which prompted us to
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Figure 4. UV-vis spectra of MOF uptake experiments with dyes: (a) 10 ppm of MLB+, (b) 10 ppm of OG2-, and (c) mix of MLB+ and OG2-
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in
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in
the
presence
of
Fe-HAF-1
over
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‡These authors contributed equally.
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ACKNOWLEDGMENT
We thank I. Tran for XPS experiments. J.B.B., J.Z. and F.A.T.
were supported by the U.S. Department of Energy (Division of
Materials Sciences, Office of Basic Energy Sciences; DE-
SC0003844; for ligand design, synthesis, structural analyses);
R.H.S. was supported by an NIH CBI Training Grant
(T32GM112584); M.K. and S.M.C. were supported by the
National Science Foundation under Award No. CHE-1661655
(ligand design, gas sorption, TGA analysis). M.K. was
additionally supported by the Department of Defense through the
National Defense Science and Engineering Graduate Fellowship
Program and an Achievement Rewards for College Scientists
Foundation Fellowship. This research used Beamline 11-BM of
the Advanced Photon Source, a U.S. Department of Energy Office
of Science User Facility operated for the DOE Office of Science
by Argonne National Laboratory under Contract No. DE-AC02-
06CH11357. XPS work was performed at the UC Irvine Materials
Research Institute using instrumentation funded in part by the
National Science Foundation Major Research Instrumentation
Program under grant no. CHE-1338173.
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