Topology-Guided Stepwise Insertion of Three Secondary Linkers in Zirconium Metal-Organic Frameworks

Article abstract of DOI:10.1021/jacs.8b04277

We report a topology-guided, precise insertion of three distinct secondary linkers into a zirconium-based metal-organic framework, NPF-300. Constructed from a tetratopic linker L and Zr₆ cluster, NPP-300 exhibits a unique scu topology and certain flexibility along the crystallographic a axis, and in conjunction with the conformation change of the primary ligand, is able to accommodate the stepwise insertion of three different secondary linkers along the a and c axes. Size-matching and mechanic strain of the resulting framework are two important factors that determine the chemical stability of the inserted linkers. Secondary linker insertion in NPF-300 significantly enables not only its porosity but also potentials to install up to three different functional groups for the construction of multivariate MOFs with homogeneity.

Full text of DOI:10.1021/jacs.8b04277

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Article
Topology-Guided Stepwise Insertion of Three Secondary
Linkers in Zirconium Metal-Organic Frameworks
Xin Zhang, Brandon L Frey, Yu-Sheng Chen, and Jian Zhang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b04277 • Publication Date (Web): 28 May 2018
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Topology-Guided Stepwise Insertion of Three Secondary Linkers in
Zirconium Metal-Organic Frameworks
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Xin Zhang,† Brandon L. Frey,† Yu-Sheng Chen,‡ and Jian Zhang*,†
†Department of Chemistry, University of Nebraska−Lincoln, Lincoln, Nebraska 68588, United States
‡ChemMatCARS, Center for Advanced Radiation Sources, The University of Chicago, 9700 South Cass Avenue, Argonne, Illinois
60439, United States
ABSTRACT: We report a topology-guided, precise insertion of three distinct secondary linkers into a zirconium-based
metal-organic framework, NPF-300. Constructed from a tetratopic linker L and Zr6 cluster, NPP-300 exhibits a unique scu
topology and certain flexibility along the crystallographic a axis, and in conjunction with the conformation change of the
primary ligand, is able to accommodate the step-wise insertion of three different secondary linkers along the a and c axes.
Size-matching and mechanic strain of the resulting framework are two important factors that determine the chemical
stability of the inserted linkers. Secondary linker insertion in NPF-300 significantly enables not only its porosity but also
potentials to install up to three different functional groups for the construction of multivariate MOFs with homogeneity.
stepwise ligand insertion appears to be a more reliable
approach.10 Recently, the Zhou group and the Su group
utilizes the sequential linker installation (SLI) (or
postsynthetic variable spacer installation, PVSI) to insert
two different secondary linkers (SLs) in a stepwise fashion
into a class of elastic PCN-700 (or LIFM-28) series.11 De-
spite the exciting progress, incorporating three distinct
SLs within one framework remains a challenge and, to the
best of our knowledge, has not been reported.
INTRODUCTION
Metal-organic frameworks (MOFs) are inorganic-
organic hybrid materials constructed via the self-assembly
of judiciously selected organic and inorganic building
blocks.1 As an emerging class of nanoporous solids with
modular nature,2 MOFs exhibit predictable topology, tai-
lorable porosity, and tunable functionality, and are suited
for a wide range of applications including gas storage,
catalysis, and sensing, to name a few.3 To further broaden
the utility of MOFs, it is important to increase the com-
plexity and/or introduce synergistic effects without com-
promising their ordered structure.4 One synthetic strategy
is to introduce “heterogeneity within order”,5 a concept
developed by Yaghi and co-workers, who have demon-
strated the facile incorporation of up to eight distinct
linkers with similar length but different functionalities
into one single framework.6 Despite the lack of
knowledge of the exact location of each functional group
due to the disordered distribution within the framework,
the resulted multivariate MOFs (MTV-MOFs) can exhibit
enhanced properties in gas adsorption7 and multifunc-
tional heterogeneous catalysis8 compared to their proto-
typic framework.
Herein, we disclose the construction of a new series of
MTV-MOFs with homogeneity via a topology-guided
stepwise insertion of three different SLs within a proto-
typic Zr-MOF (NPF-300, NPF = Nebraska Porous Frame-
work) (Figure 1). Assembled from a planar tetratopic pri-
mary linker L and eight-connected Zr6O4(OH)8(H2O)4
clusters, NPF-300 exhibits the unique scu topology. Upon
the removal of the OH–/H2O ligands of the Zr6 clusters, a
secondary linear dicarboxylate linker with an appropriate
length can be first inserted into the framework along the
a axis (Figure 1c). Next, the in-plane and out-of-plane
bending flexibility of the primary linker L enables the
stepwise insertion of two other SLs along the c axis. De-
tailed stability evaluations reveal that the size-matching
and the framework strain are two important factors that
dictate the interplay between the thermodynamics and
kinetics of the linker insertion and dissociation. Overall,
this topology-guided secondary linker insertion enables
the permanent porosity of NPF-300 and the potentials for
the installation of multiple functionalities in a new proto-
type of MTV-MOFs.
Another strategy to achieve a higher degree of func-
tionality of MOFs is to place multiple topologically dis-
tinct linkers at the precise positions in the crystalline lat-
tice, i.e., to construct MTV-MOFs with homogeneity. Alt-
hough this objective can be achieved via a one-pot, mixed
linker strategy where distinct linkers are simultaneously
incorporated into one framework,9 the postsynthetic
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Figure 1. (a) Primary tetratopic linker L and Zr6 cluster, their topological representation (C, gray; O, red, Zr, cyan), and structure
of NPF-300. (b) The augmented scu topology. (c) Schematic illustration of the step-wise insertion of three SLs. (d) Structure of
the six SLs used in this study.
(designated as NPF-300-LT) reveals a 10% decrease of
the crystallographic a axis and 2.2% and 1% increase of
RESULTS AND DISCUSSION
Tetratopic ligand H4L was synthesized via the typical
Suzuki, Sonogashira, and Glaser coupling followed by
saponification in basic aqueous solution (see Supporting
Information, S-2, for detailed procedure). Light-yellow
crystals of NPF-300 were obtained via a solvothermal
reaction of ZrCl4 with H4L in dimethylformamide
(DMF):dimethylacetamide (DEF) (v:v = 8:1) with benzo-
ic acid as the modulating agent at 120 °C for 48 h. Sin-
gle-crystal X-ray diffraction (sc-XRD) study at room
temperature reveals that NPF-300 crystallizes in the
orthorhombic crystal system with a Cmmm space group.
Each tetratopic ligand L is connected to four Zr6 clusters
that are organized in a C-centered orthorhombic ar-
rangement (Figure S16, Supporting Information). Each
Zr6 cluster is coordinated with eight L linkers with four
above and four below the equatorial plane and eight
terminal H2O/OH– groups in the equatorial plane (Fig-
ure S17), which gives the overall formula of NPF-300 as
Zr6O4(OH)8(H2O)4L2. The combination of the large size
of linker L and the unique scu topology12 results in four
large 1D open channels in NPF-300, namely, rhombic
channels of with a size of 27×15 Å along the c axis,
rhombic channels with a size of 9×13 Å along the b axis,
rhombic channels of with a size of 8×9 Å and hexagonal
channels with a diameter of 15 Å along a axis (Figure
S13-S15).
the b and c axes, respectively, as well as an overall 7.0%
decrease of unit cell volume (Figure 2b, Table S1). A Hf-
MOF (NPF-300(Hf)) also exhibits similar cell parame-
ters at 110 K (Table S1). A close examination of the crys-
tal structure shows that the temperature-dependent
deformation is mainly due to the subtle change of the
The powder XRD pattern of the solvated NPF-300 ex-
hibits an excellent agreement with the simulation, con-
firms the bulk purity of the material (Figure 2a). Inter-
estingly, a second sc-XRD study of NPF-300 at 110 K
Figure 2. (a) Experimental and simulated powder XRD
patterns of NPF-300 and NPF-300-LT. (b) Structure of NPF-
300 and NPF-300-LT viewed from the c axis.
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conformation of ligand L: the dihedral angle between
cessfully obtained the single crystals of NPF-300-2
(Scheme 1, Step II). NPF-300-2 crystalizes in the Immm
space group, and its unit cell is nearly doubled com-
pared to NPF-300 and NPF-300-1 due to the alternating
arrangement of sLa between the adjacent Zr6 clusters
along the c axis. Thus, each Zr6 cluster is 11-connected to
eight primary L, two sLc, and one sLa, with the overall
1
2
3
4
5
6
7
8
the terminal and the center phenyl rings of L in NPF-
300 and NPF-300-LT is 42.2° and 39.6°, respectively
(Figure S18), which results in a small flexibility of NPF-
300 crystals along the a axis.Zr-MOFs consisting 8-
connected Zr6O4(OH)8(H2O)4 clusters are ideal plat-
forms for SL insertion via the replacement of OH−/H2O
groups on the clusters.11,13 Encouraged by the small flexi-
bility of NPF-300 along the a axis, we first tested the
possibility to insert linker sLc as the 1st SL since its
length (15.4 Å) is close to the O-O distance between the
adjacent Zr6 clusters along the a axis (14.5 Å) (Scheme 1,
Step I). Briefly, NPF-300 crystals were placed in the solu-
tion of sLc in DMF at 60 °C for 24 h, and the resulting
crystalline material, termed as NPF-300-1, crystallizes in
the same Cmmm space group as NPF-300 and displays
the presence of sLc at the expected position. In NPF-
300-1, each Zr6 cluster is 10-connected to eight primary L
and two secondary sLc linkers, with the overall composi-
tion of Zr6O4(OH)6(H2O)2(L)2(sLc), which is confirmed
composition of Zr6O4(OH)5(H2O)(L)2(sLc)(sLa) , which
½
was confirmed by 1H NMR (vide infra, Table 1 and Figure
S6).14 Remarkably, the O-O distance between the adja-
cent 11-connected Zr6 clusters in NPF-300-2 along the c
axis is 14.5 Å, suitable for the insertion of a 3rd SL sLb
with a length of 13.8 Å, which yielded NPF-300-3
(Scheme 1, Step III). The space group of NPF-300-3 re-
mains as Immm, and each Zr6 cluster is now 12-
connected to eight primary L and two sLc, one sLa, and
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one
sLb
with
the overall
composition
of
Zr6O4(OH)4(L)2(sLc)(sLa) (sLb) ., which is confirmed by
½
½
1H NMR (vide infra, Table 1 and Figure S7). Powder XRD
analysis also confirms the bulk crystallinity of NPF-300-
2 and NPF-300-3 (Figure S22-S23).
1
by H NMR of a digested sample (vide infra, Table 1 and
Figure S5). The powder XRD patterns reveal the crystal-
linity of the bulk material and confirm the nature of
single-crystal-to-single-crystal transformation (Figure
S21).
The successful stepwise insertion of three distinct SLs
in NPF-300 benefits from the unique scu topology and
relatively large size of the primary tetratopic ligand L
that offers unique spaces to accommodate linker inser-
tion. More importantly, the flexibility of the phenyl–
alkynyl–alkynyl–phenyl backbone of the primary ligand
plays an important role. A close comparison of molecu-
lar geometry of L in NPF-300-1 and NPF-300-2 reveals a
small but critical out-of-plane and in-plane distortion,
indicated by the change of the dihedral angle between
two central phenyl planes from 0° to 11.1° and the change
of symmetry from C2 to Cs (Figure 3). Such distortion is
caused by the half occupancy of sLa within the empty
space along the c axis and offers the possibility of the
third SL insertion.
Scheme 1. Stepwise Insertion of SL in NPF-300
Figure 3. The top and side views of the conformation of
primary linker L in NPF-300-1 (a) and NPF-300-2 (b) show-
ing the in-plane and out-of-plane distortion.
It should be noted that the length of SL and the se-
quence of insertion is essential to
a successful
Upon the insertion of 1st SL sLc, the O-O distance be-
tween the adjacent 10-connected Zr6 clusters along the c
axis is 12.8 Å, close to the length of the linear ditopic
linker sLa (11.3 Å). We then used sLa as the 2nd SL for the
insertion in NPF-300-1 using a similar method and suc-
insertion.11a For instance, inserting a slightly longer link-
er sLb instead of sLa as the 2nd SL into NPF-300-1 results
in its complete occupancy along the a axis (Scheme 1,
Step IV). The resulting single crystal material, termed as
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Table 1. Chemical stability of NPF-300 MTV-MOFs
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molar ratio
L:sLc
theoretical value
as prepareda
2.00:1.00
2.00:1.10:0.92e
2.00:0.97:0.52:0.58
2.00:1.04:1.05
2.00:1.99
watera,b
2.00:1.00
2.00:1.04:0.79e
2.00:1.00:0.49:0.57
2.00:1.04:0.98
2.00:1.51
pH = 11a,c
2.00:1.00
2.00:1.07:0.76e
2.00:1.01:0.46:0.56
2.00:1.03:0.93
2.00:1.16
pH = 1a,d
2.00:1.04
2.00:0.71:0.61e
2.00:0.67:0.10:0.27
2.00:0.16:0.43
2.00:0.49
NPF-300-1
NPF-300-2
NPF-300-3
NPF-300-4
NPF-300-5
2:1
2:1:0.5
2:1:0.5:0.5
2:1:1
L:sLc:sLa
L:sLc:sLa:sLb
L:sLc:sLb
L:sLb
2:2
aMolar ratios were calculated by comparing the characteristic peaks of samples digested in K3PO4 solution in 1H NMR, as shown in Figure
S41-S44. A standard deviation of 10% was estimated based on three measurements. Samples soaked in water. Samples soaked in solu-
9
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c
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d
e
tions with pH values adjusted by HCl. Samples soaked in solutions with pH values adjusted by NaOH. The values are higher than the
expected value (0.5), indicating the additional binding of sLa along the c axis, most likely via one of the carboxyl groups.
NPF-300-4,
has
a
composition
of
these two MOFs are more kinetically controlled and
significantly dissociate especially in acidic solution (Ta-
ble 1). Lastly, the dissociation of sLa and sLb also causes
the simultaneous detachment of sLc. Specifically, in
contrast to its high stability in NPF-300-1, sLc partially
dissociates in NPF-300-2 and NPF-300-3 in acidic condi-
tion (e.g. L:sLc ratio decreases from 2.00:1.04 to 2.00:0.71
and 2.00:0.67, respectively).
Zr6O4(OH)4(L)2(sLa)(sLb). Moreover, the attempted in-
sertion of sLb first along the c axis in NPF-300 was not
successful and instead led to the simultaneous linker
insertion along both a and c axes and yielded NPF-300-
5, a framework with the overall composition of
Zr6O4(OH)4(L)2(sLb)2 (Scheme 1, Step V). This is likely
due to the intrinsic flexibility of NPF-300 for accommo-
dation of sLb (13.8 Å) in all three positions. Similarly, H
NMR and powder XRD analysis confirmed the composi-
tion and bulk crystallinity. (Table 1 and Figure S24-S25).
1
Overall, in contrast to PCN-700 and LIFM-28 series
where the dynamic twisting of the primary ligand plays
an essential role in the insertion and water-promoted,
facile dissociation of SLs,9a the ligand insertion in NPF-
300 series is more based on size-matching, which exerts
less mechanical strain on the primary framework and
results in the significantly improved stability of NPF-300
series in aqueous solutions. In particular, with the inser-
tion of a size-matched linker and the least amount of
strain, NPF-300-1 exhibits excellent resistance toward
acidic and basic conditions.
With the MTV-MOF materials in hand, we next as-
sessed their thermal stability via thermogravimetric
analysis. All MOFs exhibit a high decomposition tem-
perature around 450-500 °C, indicating their good
thermal stability at elevated temperature (Figure S49).
Excellent crystallinity also remains after treatment in
H2O, basic (pH = 11), and acidic (pH =1) conditions (Fig-
ure S40). However, the chemical stability of NPF-300
series is better quantified by digestion analysis. This is
because the partial or complete dissociation of SLs in
MTV-MOFs does not necessarily result in a change of
We next determined the porosity parameters of NPF-
300 series. Unlike some other Zr-MOFs with scu topol-
ogy, NPF-300 loses its crystallinity upon desolvation
(Figure S20).12c,12f-i,15 Even after the activation by super-
critical CO2 exchange16 it only exhibits a low BET surface
area (SABET) of 419 m2/g (Table 2 and Figure S29). To our
delight, the insertion of SLs enables the permanent po-
rosity of all MTV-MOFs. In particular, NPF-300-1, with
sLc inserted along the a axis exhibits the highest
1
crystallinity. Indeed, upon digestion, H NMR spectra
revealed the dissociation of SLs to various extent. Using
the primary ligand L as the internal reference, the rela-
tive molar ratio before and after the treatments was
quantified and summarized in Table 1.
Frist, among the five MTV-MOFs, NPF-300-1 exhibits
the highest stability as indicated by the consistent L:sLc
molar ratio of ~2:1 in water, basic, and acidic conditions
(Table 1). This can be attributed to the good size-
matching of sLc and the distance between the adjacent
Zr6 clusters along the a axis. Such thermodynamic sta-
bility is also indicated by the insignificant change of
powder XRD patterns (Figure S40) and unit cell volume
(~0.4% increase) after the ligand insertion (Table S1).
Secondly, the overall stability of other four MTV-MOFs
follows the trend: water > pH = 11 > pH = 1. Except NPF-
300-5, all MTV-MOFs exhibit impressive stability in wa-
ter and basic conditions. At the same time, the chemical
stability is roughly in correlation to the deviation of the
lattice parameters from NPF-300-1. For instance, com-
pared to NPF-300-1, the unit cell volume of NPF-300-4
and NPF-300-5 increases by 2.6% and decreases by 4.7%,
respectively (Table S1). Accordingly, the inserted SLs in
Figure 4. (a) N2 gas adsorption isotherm and (b) SABET for
NPF-300 with different amount of inserted linker sLb. The
percentage was calculated using the experimentally deter-
mined value vs the theoretical amount assuming complete
insertion was obtained.
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Table 2. Porosity Parameters, Density, and N2 Uptakes for NPF-300 MTV-MOFs
1
2
3
4
5
6
7
8
NPF-300
419
NPF-300-1
3276
NPF-300-2
2963
NPF-300-3
2750
NPF-300-4
2978
1611
NPF-300-5
2565
SABET (m2 g-1)a
SAV (m2 mL-1)
Vp (cm3 g-1)
Dc (g cm-3)
109
1657
1564
1529
1449
0.26
0.456
121
1.63
1.18
1.11
1.19
1.03
0.512
853
0.528
763
0.556
715
0.541
771
0.565
669
N2 uptakec
9
aSurface area (m2 g−1) calculated from N2 adsorption at 77 K based on the BET model. cOne bar; unit of gas uptake, cm3 g–1.
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SABET of 3236 m2/g, an increase more than seven times
(Table 2 and Figure S30). The insertion additional linkers
such as sLa (in NPF-300-2) and sLb+sLa (in NPF-300-3),
albeit the retention of permanent porosity, however re-
sults in a slight decrease of SABET due to their occupation
of the free space inside the MOF cavity (Table 2 and Fig-
ure S31-S32). Among the three MTV-MOFs with full inser-
tion of SLs, NPF-300-4 exhibits the highest SABET (2978
m2/g, 16.1 % higher than NPF-300-5), which is correlated
to its largest cell volume (7.7% larger than NPF-300-5)
(Table 2 and Figure S33-S34).
secondary
linker
derived
from
DPA
(9,10-
diphenylanthracene) can also be inserted and forming
NPF-300-8 (Figure S12 and Table S1), which can be poten-
tially utilized for heterogeneous photophysical and pho-
tochemical applications.19
In summary, we have synthesized a new class of proto-
typic MTV-MOFs based on the (4,8)-connected NPF-300
series using topology as a guidance. The unique positions
of eight-connected Zr6 clusters in the scu network and
the flexibility of the tetratopic primary linker L enable the
precise insertion of up to three different distinct second-
ary linkers along the a and c axis via step-wise, single-
crystal-to-single-crystal transformation. We have revealed
that the size-matching of the inserted linker and the
framework strain are two important factors that govern
the overall stability of MTV-POFs. To the best of our
knowledge, NPF-300 represents the first structure proto-
type that has the capability to introduce three distinct
functional groups in to a single MOF in a crystallograph-
ically ordered fashion. It is our expectation that NPF-300
can be used to build multifunctional MOF materials for a
wide range of applications including gas stor-
age/separation and synergistic/cooperative catalysis.
It should be pointed out that the regioselectivity for sLb
insertion in forming NPF-300-5 is poor. It is observed
that, as the amount of sLb used in the linker insertion in
NPF-300-5 increases, the SABET of the resulting material
increases (Figure 4). Since the realization of surface area
is closely related to the linker insertion along the a axis,
the pseudo linear correlation between the SABET and the
1
ratio of inserted ligand (determined by H NMR after di-
gestion) strongly suggests that insertion along both a and
c axis occurs simultaneously. In addition, powder XRD
patterns also demonstrate the gradual change of unit cell
parameters as the ligand insertion proceeds (Figure S38).
Having established their permanent porosity, we fur-
ther tested the potential utility of NPF-300 series in gas
storage by evaluating the uptake capacity for H2, CO2, and
CH4. Thanks to their permanent porosity, all five MTV-
MOFs exhibit significantly better performance compared
to the collapsed prototypic NPF-300 (Figure S46-S48, Ta-
ble S2). In particular, NPF-300-1 shows the highest uptake
for H2 (1.7 wt% at 77 K), CO2 (15 wt% at 273 K), and CH4
(1.4 wt% at 273 K), due to its largest surface area, pore
volume, and lowest density (Table 2). It is interesting that
at low pressure (0-40 mmHg), the CO2 adsorption of
NPF-300-2 is the highest among all (Figure S48), which is
likely due to the strong interaction between CO2 and the
extra dangling sLa we proposed to account for its high
ratio. It is foreseeable that the current moderate perfor-
mance can be readily improved via further functionaliza-
tion of the secondary linkers such as sLc and sLa to
achieve enhanced gas adsorption capability as well as se-
lectivity.11b,11e Other functional SLs with metal chelating
group can also be incorporated in NPF-300. For example,
we were able to insert catechol-17 and bipyridine-based18
SLs (i.e., sLd and sLe) and obtained the corresponding
NPF-300-6 and -7, respectively (Figure S10-S11 and Table
S1). The similar length of sLd and sLe to sLc enables inser-
tion along the a axis as such in NPF-300-1. Similarly, sLf, a
ASSOCIATED CONTENT
Supporting Information.
The Supporting Information is available free of charge on the
ACS Publications website.
Materials, general experimental procedures, synthesis of
NPF-300 series, characterizations of compounds, and crystal-
lographic data.
AUTHOR INFORMATION
Corresponding Author
*jzhang3@unl.edu
Notes
Any additional relevant notes should be placed here.
ACKNOWLEDGMENT
J.Z. acknowledges a National Science Foundation CAREER
ward (DMR-1554918) for support of this research. This work
is also partially supported by NSF/CBET-1706632. ChemMat-
CARS Sector 15 is principally supported by the Divisions of
Chemistry (CHE) and Materials Research (DMR), National
Science Foundation, under grant number NSF/CHE-1346572.
Use of the APS, an Office of Science User Facility operated
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for the U.S. DOE Office of Science by ANL, was supported
under Contract No. DE-AC02-06CH11357.
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