Two Principles of Reticular Chemistry Uncovered in a Metal-Organic Framework of Heterotritopic Linkers and Infinite Secondary Building Units

Article abstract of DOI:10.1021/jacs.6b07267

Structural diversity of metal-organic frameworks (MOFs) has been largely limited to linkers with at most two different types of coordinating groups. MOFs constructed from linkers with three or more nonidentical coordinating groups have not been explored. Here, we report a robust and porous crystalline MOF, Zn₃(PBSP)₂ or MOF-910, constructed from a novel linker PBSP (phenylyne-1-benzoate, 3-benzosemiquinonate, 5-oxidopyridine) bearing three distinct types of coordinative functionality. The MOF adopts a complex and previously unreported topology termed tto. Our study suggests that simple, symmetric linkers are not a necessity for formation of crystalline extended structures and that new, more complex topologies are attainable with irregular, heterotopic linkers. This work illustrates two principles of reticular chemistry: first, selectivity for helical over straight rod secondary building units (SBUs) is achievable with polyheterotopic linkers, and second, the pitch of the resulting helical SBUs may be fine-tuned based on the metrics of the polyheterotopic linker.

Full text of DOI:10.1021/jacs.6b07267

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Communication
Two Principles of Reticular Chemistry Uncovered in a Metal-Organic
Framework of Heterotritopic Linkers and Infinite Secondary Building Units
Noelle R. Catarineu, Alexander Schoedel, Philipp Urban,
Maureen B Morla, Christopher A. Trickett, and Omar M. Yaghi
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 12 Aug 2016
Downloaded from http://pubs.acs.org on August 13, 2016
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Two Principles of Reticular Chemistry Uncovered in a Metal-Organic
Framework of Heterotritopic Linkers and Infinite Secondary Building
Units
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Noelle R. Catarineu,† Alexander Schoedel,† Philipp Urban,† Maureen B. Morla,† Christopher A. Trick-
ett,† and Omar M. Yaghi†,‡,
*
†Department of Chemistry, University of California, Berkeley; Materials Sciences Division, Lawrence Berkeley National
Laboratory; Kavli Energy NanoSciences Institute at Berkeley
‡King Fahd University of Petroleum and Minerals, Dhahran 34464, Saudi Arabia
Supporting Information
The tritopic linker PBSP (phenylyne-1-benzoate, 3-
benzosemiquinonate, 5-oxidopyridine, Figure 1a) lacks symmetry
elements (C1 point group) and supports three different coordina-
tive functionalities, benzoate, semiquinonate, and pyridonate. We
ABSTRACT: Structural diversity of metal-organic frameworks
(MOFs) has been largely limited to linkers with at most two dif-
ferent types of coordinating group. MOFs constructed from link-
ers with three or more non-identical coordinating groups have not
linked it with zinc(II) into a highly-symmetric three-dimensional
been explored. Here, we report a robust and porous crystalline
porous framework based on infinite SBUs (rods) formulated as
MOF, Zn3(PBSP)2 or MOF-910, constructed from a novel linker
Zn3(PBSP)2 and termed MOF-910. Single-crystal X-ray diffrac-
PBSP
(phenylyne-1-benzoate,
3-benzosemiquinonate,
5-
tion revealed that this MOF crystallizes in the trigonal space
oxidopyridine) bearing three distinct types of coordinative func-
tionality. The MOF adopts a complex and previously unreported
topology termed tto. Our study suggests that simple, symmetric
linkers are not a necessity for formation of crystalline extended
structures and that new, more complex topologies are attainable
with irregular, heterotopic linkers. This work illustrates two prin-
ciples of reticular chemistry: first, selectivity for helical over
straight rod secondary building units (SBUs) is achievable with
polyheterotopic linkers, and second, the pitch of the resulting
helical SBUs may be fine-tuned based on the metrics of the poly-
heterotopic linker.
�
group R3c and comprises helical one-dimensional SBUs that form
hexagonal channels 21 Å in diameter (Figure 1b). MOF-910
adopts a new topology, termed tto, and it is the first example of a
MOF based on a heterotritopic linker. Construction of MOFs from
less symmetric linkers with multiple different coordinating groups
is a new method to target helical rod MOFs in which the helical
pitch is pre-determined by the linker. MOFs based on rod-like
SBUs are desirable due to their resistance to interpenetration,
potential for isoreticular expansion, and breathing functionality.4
While the discovery of helical rather than straight rod MOFs re-
lies on trial and error when symmetric, homotopic molecules
serve as the linkers,5 we find that MOFs based on helical SBUs
are the preferred products of syntheses with less symmetric link-
ers due to the non-uniform distances between the coordinating
groups. The power to impart helicity to SBUs in this way is prom-
ising for the design of non-centrosymmetric MOFs for asymmet-
ric catalysis and chiral resolution.6
To date, the majority of metal-organic frameworks (MOFs)
have been built from highly symmetric linkers that consist of one
or two types of coordinating group.1 It is believed that symmetry
and uniformity of coordinating groups in the linker facilitate as-
sembly into a crystalline extended structure of high symmetry.2
One reason for this prevailing view is that if all the coordinating
groups are identical, conditions in which bond formation to the
metals is reversible can be achieved for all of these groups simul-
taneously so that they ultimately reticulate into a crystalline rather
than amorphous phase.3 Additionally, a highly symmetric linker
has a greater probability of aligning to form a periodic structure
since its ligating groups are the same and therefore easily inter-
changeable during crystal growth. Thus, it has been an article of
faith in MOF chemistry that symmetric building units should be
employed for the synthesis of highly symmetric extended struc-
tures. However, our work demonstrates that infinite secondary
building units (SBUs) accommodate irregular polytopic linkers
into a crystalline extended structure. By examining the novel
MOF described here in the context of the MOF literature, we have
uncovered two principles of reticular chemistry involving selec-
tivity of helical over straight rod SBUs and control of SBU helici-
ty.
The three distinct coordinative functionalities of the PBSP
linker were chosen for their propensities to bind in a bidentate or
bridging fashion and for their high number of possible coordina-
tion modes.7 While benzoate moieties are ubiquitous in MOF
chemistry, semiquinonate or catecholate moieties have been in-
corporated into very few three-dimensional MOFs.8 Additionally,
a small number of MOFs are based on 2-hydroxypyrimidine,9 but
the less-symmetric derivative 2-pyridone had yet to be incorpo-
rated into an extended framework. We find the stark differences
between the pKa’s of these three groups (4.2, 9.5, and 11, respec-
tively)10 do not preclude MOF formation by one-pot solvothermal
conditions.
The neutral, closed-shell form of the heterotritopic linker,
termed PBCP (phenylyne-1-benzoic acid, 3-catechol, 5-pyridone),
was attained in three synthetic steps requiring one column purifi-
cation (Schemes S1 – S3). Solvothermal synthesis with PBCP and
ZnCl2 under basic conditions yielded 100 µm hexagonal needles
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charged state is reasonable given that catechol based linkers un-
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dergo aerobic oxidation to semiquinone radicals under similar
MOF synthesis conditions.12 The MOF channels are lined with a
double-wall built from pairs of closely associated linkers (Figure
1b). Gaps between each pair of linkers create windows in the
double-wall measuring 4.1 Å. The one-dimensional SBUs exist in
equal populations of left- and right-handed helical conformations
such that the overall structure is centrosymmetric.
The presence of three distinct bidentate coordinating groups in
the linker makes it unlikely that all metal ions in the structure
would exist in a single type of coordination environment. Indeed,
the zinc ions of this MOF adopt two configurations distinct in the
metal-link bonds involved. In two-thirds of the cases, each zinc
ion has three benzosemiquinonate oxygens, one carboxylate oxy-
gen, and one pyridonate nitrogen in its inner coordination sphere.
The other third of the zinc ions are each bound by two benzosem-
iquinonate oxygens, two pyridonate oxygens, and one carboxylate
oxygen. The linker is low enough in symmetry that the three co-
ordinating groups are non-interchangeable in the MOF structure.
Interestingly, within each closely stacked pair of linkers that lines
the channels, the pyridonate and benzosemiquinonate moieties of
one linker align with the pyridonate and semiquinonate moieties
of the partner linker while the benzoate moieties of the two linkers
align together (Figure 1c). This preferential association could
bring cooperative sidechains on linkers together in space in a
controllable manner to direct segregation of functionalities in
multivariate (MTV) MOF systems.13
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The preferential alignment of coordinating groups also instills
disparate rigidity. While the pyridonate and benzosemiquinonate
moieties are inflexible since they form two points of attachment to
the same SBU, the benzoate moiety of each linker is disordered
because it is the single point of attachment to the opposing SBU.
Specifically, each benzoate moiety adopts one of two equally
likely conformations. In one conformation, the benzoate ring is
coplanar with the central aromatic ring to which it is bonded, and
the carboxylate binds to two zinc ions in a bridging fashion. In the
other conformation, the benzoate ring is tilted with respect to the
central aromatic ring, and a single carboxylate oxygen is coordi-
nated to a zinc ion (Figure 1c).
A host of additional analytical techniques performed on MOF-
910 corroborate the structure solved by single-crystal X-ray dif-
fraction. Powder X-ray diffraction substantiates the bulk phase
purity (Figure S7). Elemental analysis of MOF-910 after activa-
tion to remove guests from the pores supports the chemical for-
mula as Zn1.5(PBSP)·2H2O (calc., C: 56.36%; H: 2.96%; N:
2.74%; found, C: 54.48%; H: 2.77%; N: 3.09%). The symmetric
resonance reflecting a g-factor of 2.050 in the solid-state electron
paramagnetic resonance spectrum is consistent with the character-
ization of the linker as a monoradical semiquinonate species (Fig-
ure S9). Fourier-transform infrared spectroscopy verifies each of
the MOF’s six ligating atoms is deprotonated (Figure S10). The
proton NMR spectrum of MOF-910 post-digestion exclusively
exhibits resonances attributable to the linker (Figure S5). The
absence of any resonances due to counterions, such as tri-
ethylammonium or dimethylammonium, confirms the chemical
composition as a neutral framework with a fully deprotonated
trianionic linker. Thermogravimetric analysis measured in air
establishes MOF-910’s high thermal stability. The residual weight
percent of ZnO reflects the chemical formula (Figure S11).
Framework decomposition does not begin until 320 °C. The
greater basicity of the benzosemiquinonate and pyridonate when
compared to the carboxylates of typical linkers likely contributes
to the high thermal stability of MOF-910.14 Maintenance of crys-
tallinity after suspension in acidic (pH 4) and basic (pH 8) aque-
ous solutions as well as a number of organic solvents (Figure S8)
demonstrates MOF-910’s good chemical stability.
Figure 1. a) PBSP heterotritopic linker. b) Structure of MOF-910
viewed along the c-axis in the direction of hexagonal channels.
Disorder in benzoate moieties is omitted for clarity. c) Coordina-
tion of PBSP heterotritopic linker to zinc ions viewed perpendicu-
lar to channels. Atom colors: Zn, light blue; C, black; O, red; N,
green; benzoate rings, purple; semiquinonate rings, yellow; pyri-
donate rings, dark blue. Hydrogen atoms are omitted for clarity.
of MOF-910 (Scheme S4). Structural elucidation by single-crystal
X-ray diffraction revealed MOF-910 belongs to the space group
�
R3c (No. 167) with lattice parameters a = b = 47.239(2) Å and c =
27.122(1) Å. It is notable that the heterotritopic linker crystallizes
�
in a space group belonging to the Laue class 3m despite the lack
of symmetry usually imparted by the linker in MOF syntheses.11
Although the three ligating groups are quite different in acidi-
ty and MOF synthesis commences with the linker in its neutral,
protonated form, each of the three coordinating groups forms
bonds to metal ions in the extended structure. The asymmetric
unit includes one linker molecule and two distinct zinc atoms, one
on a general position in the unit cell and the other on a two-fold
rotational axis. This composition corresponds to the chemical
formula Zn3(PBSP)2. The metal to linker molar ratio and the
knowledge that +2 is the only common oxidation state of zinc
imply the linker exists as a trianion in the MOF structure. This
2
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The N2 adsorption isotherm at 77 K confirms MOF-910’s
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permanent porosity and that its pores are free of counterions. The
Type IV profile and step at a relative pressure of P/P0 = 0.075
verifies the presence of a mesopore (Figure S12).15 A Brunauer-
Emmett-Teller (BET) surface area of 2,120 m2 g-1 was derived
from the sorption isotherm and matches the expected value of
2,100 m2 g-1 derived from the single-crystal structure. The calcu-
lated pore size distribution indicates a single pore width that
matches well with the van der Waals pore diameter of 21 Å de-
termined by single-crystal X-ray diffraction (Figure S13).
9
For the remainder of this contribution, we describe how MOF-
910 uncovers two principles of reticular chemistry. Topologically,
MOF-910 is an embedding of a new net with the RCSR symbol
tto (triangles, tetrahedra, octahedra).16 The structure has six
points of extension: three located within the central aromatic ring
of the linker and three more located at the branching points of
each bidentate coordinating group. Connecting the three points of
extension within the central ring of each linker reduces this part of
each linker to a triangle (Figure 2a). Connecting the points of
extension within each coordinating group to those of neighboring
linkers reduces the SBUs to helices in which octahedra share fac-
es with the neighboring tetrahedra and tetrahedra share edges with
other tetrahedra (Figure 2b). MOF-910 is the first structure with a
topology based on an SBU of this kind. It is interesting to note
that although the high number of nodes makes this net complex, it
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�
has high symmetry (R3c, Figure 2c).
Despite two decades of research, the field of MOFs remains
lacking in the ability to predict and target structures based on
building units.17 In contrast to the organic constituents of MOFs,
which are based on linkers that serve as pre-formed building units
that remain largely unchanged during MOF synthesis, a major
challenge is control of the metal-based components of MOFs.
Recent efforts to target MOFs based on a specific discrete SBU
rely on the pre-synthetic growth of metal clusters prior to linkage
into an extended structure.18 However, such a strategy is not pos-
sible with infinite SBUs. Thus, selectivity for a MOF built from a
particular type of infinite SBU is an unsolved problem.
Analysis of MOF-910 provides insights for addressing these
challenges. The metrics and coordination modes of the three ligat-
ing groups of the PBSP linker are markedly dissimilar, yet the
linker reticulates into a symmetric, porous, and crystalline extend-
ed structure by way of infinite SBUs. Indeed, the structure con-
sists of a single type of infinite SBU that satisfies the disparate
requirements of the three links (Figures 2b and c). Due to the lack
of trigonal symmetry in the PBSP linker, the distance between the
semiquinonate and pyridonate coordinating groups is shorter than
the distance from either moiety to the carboxylate. For this reason,
the semiquinonate and pyridonate bond to zinc ions of the same
one-dimensional SBU. This two-point attachment of the linker to
a single SBU directs the formation of helical rather than straight
rods. The coordination behavior of this heterotritopic linker con-
trasts with that of BTB (benzene-1,3,5-triyl-tribenzoate), a higher
symmetry tritopic linker with a three-fold rotational axis. BTB
forms straight rods rather than helices since no two coordinating
groups bind to the same SBU (Figure 3a).19 Indeed, the PBSP
heterotritopic linker reported here is more similar to BPT (bi-
phenyl-3,4',5-tricarboxylate), a desymmetrized derivative of BTB
that forms straight rods when each of the three carboxylates coor-
dinates to a different SBU20 and helical rods when the two proxi-
mal carboxylates bind to the same SBU (Figure 3b).21 Only two
other MOFs, Fe(BDC) (BDC = 1,4-benzenedicarboxylate) and
MOF-73, feature SBUs similar to those of MOF-910 comprising
pairs of tetrahedra alternating with octahedra (Figure 3c). Howev-
er, these SBUs are straight rather than helical rods because the
linkers are ditopic rather than non-trigonal tritopic, as is the case
with the PBSP heterotritopic linker.22,23 We therefore identify a
Figure 2. Deconstruction of MOF-910 for topological analysis.
(a) PBSP heterotritopic linker is reduced to a triangle. b) Points of
extension are connected to reduce SBU to a helical rod composed
of octahedra alternating with pairs of tetrahedra. (c) tto topology.
tenet of reticular chemistry from this work in the context of the
MOF literature: choice of a polytopic linker in which the distances
between the coordinating groups are non-uniform facilitates the
formation of helical over straight rod SBUs.
Another design element is the pitch of a helical SBU. The in-
tramolecular distance between the coordinating atoms of the sem-
iquinonate and pyridonate define the pitch of the MOF-910 SBUs
as 27.122(1) Å or one unit cell length along the c-axis. The heli-
ces are three-fold symmetric since the six linkers that provide the
twelve coordinating groups present in one complete turn propa-
gate in three directions. Four-fold helices would be possible with
a greater semiquinonate to pyridonate distance. Conversely, a
shorter distance between the semiquinonate and pyridonate could
yield a single-walled structure with three- or four-fold symmetry.
In this way, researchers can fine-tune the separation between the
two coordinating groups that bind to the same SBU to produce a
MOF with SBUs of a desired helical pitch. This realization eluci-
dates a second guiding principle of reticular chemistry: the dis-
tance between the two proximal coordinating groups of a polyhet-
erotopic defines the pitch of a helical SBU. We note that the two
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Figure 3. Effect of linker symmetry on SBU helicity. a) Tritopic
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derivative
of
BTB
linker
produces
straight
rods
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BDC produces straight rods [Fe(BDC) and MOF-73].
principles of reticular chemistry exposed by MOF-910 and de-
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known rod MOFs.24
ASSOCIATED CONTENT
Supporting Information
The supporting information is available free of charge on the ACS
Publications website at DOI: xx.xxxx
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Synthesis, NMR, SEM, X-ray diffraction, EPR, IR,
TGA, N2 adsorption, and optical microscopy data (PDF)
Single-crystal X-ray diffraction data (CIF)
AUTHOR INFORMATION
Corresponding Author
*yaghi@berkeley.edu
Notes
The authors declare no competing financial interests.
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ACKNOWLEDGMENT
Financial support for this work was provided by BASF SE (Lud-
wigshafen, Germany). N.R.C. thanks the NSF for a Graduate
Research Fellowship and the UC Berkeley Graduate Division for
a Chancellor’s Fellowship. A.S. and P.U. acknowledge the Ger-
man Research Foundation (DFG, PU 286/1-1 and SCHO 1639/1-
1) for financial support. We thank Wenjia Ma and Elena López-
Maya for technical assistance with MOF synthesis, Drs. Adam
Duong, Michael O’Keeffe, and Hans-Beat Bürgi for useful dis-
cussions, Dr. Ruchira Chatterjee for assistance with EPR meas-
urements, and Drs. Kevin J. Gagnon and Simon J. Teat for help
collecting single-crystal X-ray diffraction data at Beamline 11.3.1
of the Advanced Light Source at Lawrence Berkeley National
Lab, which is supported by the Director, Office of Science, Office
of Basic Energy Sciences, of the U.S. Department of Energy un-
der Contract No. DE-AC02-05CH11231.
(24) Schoedel, A.; Li, M.; Li, D.; O’Keeffe, M.; Yaghi, O. M. Chem.
Rev. In press.
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