Amine-Tagged Fragmented Ligand Installation for Covalent Modification of MOF-74

Article abstract of DOI:10.1002/anie.202100456

MOF-74 is one of the most explored metal–organic frameworks (MOFs), but its functionalization is limited to the dative post-synthetic modification (PSM) of the monodentate solvent site. Owing to the nature of the organic ligand and framework structure of MOF-74, the covalent PSM of MOF-74 is very demanding. Herein, we report, for the first time, the covalent PSM of amine-tagged defective Ni-MOF-74, which is prepared by de novo solvothermal synthesis by using aminosalicylic acid as a functionalized fragmented organic ligand. The covalent PSM of the amino group generates metal binding sites, and subsequent post-synthetic metalation with Pd^II ions affords the Pd^II-incorporated Ni-MOF-74 catalyst. This catalyst exhibits highly efficient, size-selective, and recyclable catalytic activity for the Suzuki–Miyaura cross-coupling reaction. This strategy is also useful for the covalent modification of amine-tagged defective Ni₂(DOBPDC), an expanded analogue of MOF-74.

Full text of DOI:10.1002/anie.202100456

Angewandte
Communications
Chemie
How to cite: Angew. Chem. Int. Ed. 2021, 60, 9296–9300
International Edition:
German Edition:
doi.org/10.1002/anie.202100456
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Metal–Organic Frameworks
Hot Paper
Amine-Tagged Fragmented Ligand Installation for Covalent Modifi-
cation of MOF-74
Jaewoong Lim, Seonghwan Lee, Hyeonbin Ha, Junmo Seong, Seok Jeong, Min Kim,
Seung Bin Baek,* and Myoung Soo Lah*
Abstract: MOF-74 is one of the most explored metal–organic
frameworks (MOFs), but its functionalization is limited to the
dative post-synthetic modification (PSM) of the monodentate
solvent site. Owing to the nature of the organic ligand and
framework structure of MOF-74, the covalent PSM of MOF-
74 is very demanding. Herein, we report, for the first time, the
covalent PSM of amine-tagged defective Ni-MOF-74, which is
prepared by de novo solvothermal synthesis by using amino-
salicylic acid as a functionalized fragmented organic ligand.
The covalent PSM of the amino group generates metal binding
sites, and subsequent post-synthetic metalation with PdII ions
affords the PdII-incorporated Ni-MOF-74 catalyst. This cata-
lyst exhibits highly efficient, size-selective, and recyclable
catalytic activity for the Suzuki–Miyaura cross-coupling reac-
tion. This strategy is also useful for the covalent modification of
amine-tagged defective Ni2(DOBPDC), an expanded ana-
logue of MOF-74.
adjacent functionalized DOBDCs, inhibiting the formation
of the isoreticular framework. Therefore, no covalent PSM of
MOF-74 has been reported so far.
Herein, we report, for the first time, the covalent
modification of amine-tagged defect-engineered Ni-MOF-74
(DEMOF-I) and Ni2(DOBPDC)[14] (DEMOF-II, Scheme 1;
DOBPDC4À = 4,4’-dioxido-3,3’-biphenyldicarboxylate). The
introduction of amino groups into the MOF was achieved
by direct solvothermal synthesis using n-aminosalicylic acid
(H2n-aSA) as a fragmented organic ligand. The amine-tagged
DEMOF-I retains its crystallinity and permanent porosity
even with defect sites in the framework. Below the approxi-
mated 20% doping level of n-aminosalicylate (n-aSA), all the
MOFs showed an improved adsorption capacity for N2. By
covalent PSM, the amino group of DEMOF-I was converted
into an iminopyridine group by reaction with pyridine
aldehyde. Subsequent post-synthetic metalation produced
a PdII-incorporated catalyst. The catalyst showed highly
M
OF-74 is one of the most studied metal–organic frame-
works (MOFs) because it is highly stable in various solvents
and has a high density of potential open metal sites in the
framework.[1–6] The dative post-synthetic modification (PSM)
of the MOF-74 monodentate solvent site (i.e. the potential
open metal site) has given it enhanced performance in various
applications, such as gas storage,[7] selective separation,[8] and
proton conductivity.[9] However, only a few applications in
solution have been reported[10–12] because the ligand bound to
the open metal site is released in the solution,[13] nullifying the
dative PSM. The covalent PSM of MOF-74 is expected to give
MOF-74 new physical and chemical properties that have not
been reported so far, which will open up new opportunities in
unexplored fields. However, the covalent PSM of MOF-74 is
challenging because the synthesis of functionalized 2,5-
dioxido-1,4-benzenedicarboxylic acid (H4DOBDC) is very
difficult. Moreover, the introduction of functionalized
DOBDC is likely to increase steric hindrance between
[*] J. Lim, S. Lee, J. Seong, Dr. S. Jeong, Prof. Dr. S. B. Baek,
Prof. Dr. M. S. Lah
Department of Chemistry
Ulsan National Institute of Science and Technology (UNIST)
Ulsan 44919 (Republic of Korea)
E-mail: sbbaek@unist.ac.kr
mslah@unist.ac.kr
H. Ha, Prof. Dr. M. Kim
Department of Chemistry, Chungbuk National University
Cheongju 28644 (Republic of Korea)
Scheme 1. Covalent modification and metalation of DEMOF-I (or
DEMOF-II) prepared by a de novo solvothermal reaction by employing
the mixed ligands DOBDC (or DODPDC) and an amine-tagged frag-
ment, and the Suzuki–Miyaura cross-coupling reaction using Pd-
incorporated DEMOF-I as a heterogeneous catalyst.
Supporting information and the ORCID identification numbers for
some of the authors of this article can be found under:
https://doi.org/10.1002/anie.202100456.
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efficient, size-selective, and recyclable catalytic performance
for the Suzuki–Miyaura cross-coupling reaction of phenyl-
boronic acid and a series of aryl bromides.
A fragmented ligand is often used either as a modula-
tor[15,16] or as a defect-generating dopant[16–18] during the
synthesis of MOFs. Since MOF-74 does not allow function-
alized DOBDC in the framework, we used a functionalized
DOBDC fragment as a dopant during the de novo synthesis
of the amine-tagged defective MOF-74. Recently, several
mixed-ligand M-MOF-74 (M = Mg, Mn, Co, and Ni) deriva-
tives have been synthesized by doping 2-hydroxy-1,4-benze-
nedicarboxylate (BDC-OH).[19–21] Conversely, fragmented
carboxylate ligands without hydroxy groups can only be
doped into the framework at very low concentrations. This
suggests that the two functional groups of DOBDC, namely
-OH and -COOH, are required to participate simultaneously
in the assembly of the mixed-ligand M-MOF-74. However,
attempts to coassemble salicylate (SA) in Mn-MOF-74 was
not successful.[20] Meanwhile, in the reaction of zinc and
H4DOBDC in the presence of salicylic acid (H2SA), the H2SA
only acted as a modulator, and Zn-MOF-74 grew in the form
of a nanosized rod.[22] With this information, we attempted to
find doping conditions, using H2SA as a fragmented ligand,
since many salicylic acid derivatives with diverse functional
groups are available. As functionalized fragments, we judi-
ciously chose 5- and 3-aminosalicylic acid because an amino
group is suitable for further covalent PSM with many organic
functional groups.[23,24]
All attempts to incorporate an SA, as a fragmented ligand,
into the framework of M-MOF-74 (M = Mg, Mn, Co, and Zn)
were unsuccessful (Figures S1 and S2). In contrast, in the case
of Ni-MOF-74, the SA-incorporated DEMOF-I (I-SAx,
where I and x represent Ni-MOF-74 and the mole fraction
of the integrated SA at the DOBDC ligand sites of the
framework, respectively) was successfully synthesized in
a DMF/EtOH/H2O (15:1:1, v/v/v) solvent mixture (Figures
S3–S10). This approach is also effective for introducing 3-aSA
or 5-aSA into the framework of Ni-MOF-74, thereby resulting
in amine-tagged DEMOF-I (denoted as I-n-aSAx, where n-
aSA and x represent the integrated n-aSA and the mole
fraction of the integrated n-aSA at the DOBDC sites of the
framework, respectively). I-SAx and I-5-aSAx retained good
crystallinity up to a fragment mole fraction of approximately
20% (Figures 1a, S5, and S11), whereas I-3-aSAx retained its
crystallinity, but its crystallinity was inferior to I-SAx and I-5-
aSAx (Figures S6, S12, and S13).
Figure 1. a) PXRD patterns and b) N2 sorption isotherms of Ni-MOF-
74 and I-5-aSAx at 77 K.
was the same as that of the pristine Ni-MOF-74. This finding
is related to the increase in the number of defect sites.
The amino group on I-5-aSA0.20 can be covalently
modified through a Schiff-base condensation reaction. The
reaction of I-5-aSA0.20 with 2-formylpyridine produced I-5-
pSA0.20 containing a 5-(pyridin-2-ylmethylene)amino group
(Figure S17a). The Pd-incorporated DEMOF-I, I-5-pSA0.20
-
Pd0.05, can be obtained through post-synthetic metalation.[25]
The Pd-incorporated MOFs preserved their crystallinity after
the entire PSM procedure (Figure 2a). Transmission electron
microscopy (TEM) and energy-dispersive spectroscopy
(EDS) showed that the Pd atoms were considerably dispersed
in I-5-pSA0.20-Pd0.05 (Figure 2c–e). I-3-pSA0.18 and I-3-pSA0.18
-
Pd0.07 can also be obtained by the same procedure using I-3-
aSA0.18 (Figures S17b, S18, and S19). X-ray photoelectron
spectroscopy (XPS) data support the presence of PdII ions in
I-3-pSA0.18-Pd0.07 (Figure S20). The covalent PSM of the
amine-tagged DEMOF-I and subsequent metalation of the
framework slightly reduced the pore volume of the corre-
sponding MOF (Figures 2b, S21a, and Table S1). The doping
of n-aSA led to a significant broadening of the pore-size
distribution of the MOFs (Figures S21b and S22), which
suggests that the enlargement and reduction of the local pore
dimension occurred simultaneously around the defect sites.
More interestingly, the covalent PSM had a different effect on
the pore-size distributions of the modified DEMOFs. The
functionalization of both amine-substituted SAs led to
a narrow pore-size distribution of the MOFs. Conversely,
while the functionalization of the 3-aSA residue mainly
reduced the size of the relatively large pores, the function-
alization of the 5-aSA residue predominantly reduced the size
of the relatively small pores. Thus, MOFs with different
average pore dimensions were produced. The average pore
size of I-3-pSA0.18-Pd0.07 ( ꢀ 10 ꢀ) and I-5-pSA0.20-Pd0.05
( ꢀ 12 ꢀ) is slightly smaller and larger than that of the pristine
Ni-MOF-74 ( ꢀ 11 ꢀ), respectively.
As expected, the doping of the fragment affected the
porosities of the resulting amine-tagged DEMOF-I. Interest-
ingly, the doping of 5-aSA led to an increase in the porosity of
I-5-aSAx compared to pristine Ni-MOF-74 (Figure 1b and
Table S1), even above a doping level of 30%. In contrast, the
amount of N2 absorbed in I-SAx and I-3-aSAx slightly
increased only at relatively low mole fractions of fragments
(Figures S14a, and S15a). The pristine Ni-MOF-74 and
amine-tagged DEMOF-I showed almost the same mean
pore diameters that peaked at 11 ꢀ (Figures S14b, S15b, and
S16). As the mole fraction of n-aSA increased, the pore-size
distribution became wider, while the average pore dimension
Although there are no reports of the covalent modifica-
tion of DOBPDC in Ni2(DOBPDC), an extended analogue of
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volume and pore dimensions of the functionalized and Pd-
incorporated DEMOF-II, II-5-pSA0.17 and II-5-pSA0.17-Pd0.06
.
Since the PdII-incorporated DEMOFs have a catalytic
center in the framework, we performed the Suzuki–Miyaura
cross-coupling reaction, one of the representative Pd-cata-
lyzed reactions between aryl halides and aryl boronic
acids,[29–31] to evaluate the catalytic activities of the PdII-
incorporated DEMOFs. As a model reaction, 4-bromoaniline
(substrate 1) and phenylboronic acid were selected as the
substrates to form 4-aminobiphenyl (Table 1). Whereas the
pristine Ni-MOF-74, I-5-aSA0.20 and I-5-pSA0.20, showed no
catalytic activity (entry 1), I-5-pSA0.20-Pd0.05 afforded a 99%
yield of the cross-coupled product, 4-aminobiphenyl
(entry 2). Interestingly, I-5-pSA0.20-Pd0.05 exhibited superior
catalytic activity compared to PdCl2, a commercially available
homogeneous catalyst, under the same reaction conditions.
Additionally, the catalytic activity of I-5-pSA0.20-Pd0.05 was
equivalent to that of Pd-5-pSA (entry 5), a homogeneous
model catalyst, whose structure imitates the catalytic site of I-
5-pSA0.20-Pd0.05. The catalytic activities of I-5-pSA0.20-Pd0.05
À
and I-3-pSA0.18-Pd0.07 were also examined for the C C
coupling reaction of phenylboronic acid with various aryl
bromides (Table S2). Both catalysts were highly efficient for
the reactions. The yields ranged from 72% to 99%, depend-
ing on the substrate.
Figure 2. a) PXRD and b) N2 sorption isotherms of I-5-aSA0.20
,
I-5-pSA0.20, and I-5-pSA0.20-Pd0.05. c) TEM image of I-5-pSA0.20-Pd0.05. EDS
mappings of d) Ni (green) and e) Pd (red) overlaid on the TEM image
Table 1: Pd-catalyzed Suzuki–Miyaura cross-coupling reactions.
of I-5-pSA0.20-Pd0.05
.
MOF-74, which has larger pores than MOF-74, can provide
a more efficient diffusion of a substrate or diffuse a larger
substrate into its framework than MOF-74.[14,26–28] The same
synthetic procedure was applied for the synthesis of DEMOF-
II to determine whether the synthetic strategy was valid for
the MOF-74 analogue. Following the same procedure used for
the preparations of I-SAx and I-n-aSAx (Figures S23 and S24),
amine-tagged DEMOF-II, denoted as II-SA0.10, II-5-aSA0.05
,
and II-5-aSA0.17, depending on the incorporated fragments,
was successfully synthesized using H4DOBPDC. Addition-
ally, the covalently modified DEMOF-II, II-5-pSA0.17 and II-
5-pSA0.17-Pd0.06, were prepared according to the same cova-
lent PSM procedure used for the preparation of I-5-pSA20 and
I-5-pSA0.20-Pd0.05. The pore volume of II-5-aSA0.17 was sig-
nificantly reduced compared to that of pristine Ni2-
(DOBPDC) (Figure S25a and Table S1). The reduced poros-
ity of the amine-tagged DEMOF-II might be related to the
reduced crystallinity arising from the increased number of
defect sites in the crystals. The presence of n-aSA in the
framework altered the average pore size and pore-size
distribution of the MOFs. The amine-tagged DEMOF-II
had an average pore size of 17 ꢀ, which is approximately 4 ꢀ
smaller than that of the pristine Ni2(DOBPDC) (Fig-
ure S25b). The pore-size distribution of the amine-tagged
DEMOF-II became wider and shifted towards a relatively
small dimension. This indicates that the doping of n-aSA
reduces pore dimensions around defect sites. Subsequent
functionalization and Pd metalation slightly reduced the pore
Entry
Catalyst[a]
Substrate
Yield[b] [%]
1
2
3
4
5
6
7
8
I-5-pSA0.20
I-5-pSA0.20-Pd0.05
I-3-pSA0.18-Pd0.07
II-5-pSA0.17-Pd0.06
Pd-5-pSA
PdCl2
0
99
99
71
99
60
80
30
88
19
80
53
99
99
[a]
[a]
1
2
3
2
3
2
3
2
3
I-5-pSA0.20-Pd0.05
9
[a]
I-3-pSA0.18-Pd0.07
II-5-pSA0.17-Pd0.06
Pd-5-pSA
10
11
12
13
14
[a]
[a] 1.3 mol% Pd for I-5-pSA0.20-Pd0.05; 2.0 mol% Pd for I-3-pSA0.18-Pd0.07
2.3 mol% Pd for II-5-pSA0.17-Pd0.06; 1.3 mol% Pd for the other Pd-
containing catalysts. [b] Yields were determined by 1H NMR spectros-
copy.
;
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It is well-known that heterogeneous catalysts derived
from MOFs can utilize the catalytic sites located at their outer
and inner pore surfaces.[32,33] To elucidate the locations of
active catalytic sites in the DEMOF-74 catalysts, we per-
formed Suzuki–Miyaura coupling reactions of phenylboronic
acid with aryl bromides of various molecular dimensions. The
À
C C coupling reactions of the smallest substrate 4-bromoani-
line were quantitative (entries 2 and 3), except for with II-5-
pSA0.17-Pd0.06 (entry 4), which had the largest pore dimen-
sions. The relatively low yield can be attributed to the low
density of active catalytic centers in II-5-pSA0.17-Pd0.06 com-
pared to the other catalysts investigated. For 1-bromo-3,5-
diphenylbenzene (substrate 2), where the second-largest
minimum dimension (MIN-2, 10.8 ꢀ) is similar to the pore
dimension of I-3-pSA0.18-Pd0.07, the yields ranged from 80% to
88% for the same heterogeneous catalysts (entries 7, 9, and
11). These yields contrast with the completion of the reaction
with the homogeneous catalyst Pd-5-pSA (entry 13).
The size-selectivity of the catalysts is demonstrated in the
reaction of 9,9’-(5-bromo-1,3-phenylene)bis(3,6-di-tert-butyl-
9H-carbazole (substrate 3). The molecular dimensions of
substrate 3 (MIN-2, 13.5 ꢀ) is comparable to the pore
dimensions of I-5-pSA0.20-Pd0.05 and slightly larger than that
Figure 3. a) Hot filtration and b) recycling test of I-5-pSA0.20-Pd0.05 in
the Suzuki–Miyaura cross-coupling reaction.
the reaction conditions (Figure 3b). The PXRD character-
ization of I-5-pSA0.20-Pd0.05 after catalysis further demon-
strated that the PdII-incorporated DEMOF, I-5-pSA0.20-Pd0.05
,
retained high crystallinity (Figure S26).
In summary, we have successfully demonstrated that the
synthesis of functionalized DEMOF-I and DEMOF-II deriv-
atives can be achieved by amine-tagged fragment installation.
The installation of the fragment into the framework resulted
in defective but highly stable porous MOFs. Amine-tagged
DEMOFs can be covalently modified with an aldehyde
functional group to give an iminopyridine functionality that
can be further modified by post-synthetic metalation. The Pd-
incorporated DEMOFs were highly efficient, size-selective,
and recyclable heterogeneous catalysts for the Suzuki–
Miyaura cross-coupling reaction. These results suggest that
a combination of fragment installation and subsequent
covalent PSM will become an efficient procedure to introduce
desired functionality into MOFs, and this approach will
provide great opportunities to explore many MOFs in diverse
applications.
À
of I-3-pSA0.18-Pd0.07. Additionally, the MIN-2 of the C C
coupled product was estimated to be 17.4 ꢀ, which is
considerably larger than the pore dimensions of both
catalysts. As expected, we observed drastically reduced
catalytic activities with a 30% yield for I-5-pSA0.20-Pd0.05
(entry 8) and 19% yield for I-3-pSA0.18-Pd0.07 (entry 10). The
À
C C coupling reactions were expected to occur mainly at the
catalytic sites located on the outer surface of the MOFs.
Meanwhile, the yield of the same reaction with II-5-pSA0.17
-
Pd0.06, at 53%, was significantly enhanced (entry 12) because
the catalytic sites at the outer surface and inner pore surface
of II-5-pSA0.17-Pd0.06 with an average pore size of 17 ꢀ were
more accessible to the substrate.
Acknowledgements
The leaching of metal ions from the active sites during
catalysis is a critical issue for metal-incorporated heteroge-
neous catalysts.[29,34] Therefore, a hot-filtration test was
performed using the reaction of I-5-pSA0.20-Pd0.05 to deter-
mine whether Pd ions were leached out during the reaction.
After 1 h of reaction, the catalyst I-5-pSA0.20-Pd0.05 was
removed from the reaction mixture by hot filtration, and
the filtrate was allowed to react for an additional 23 h. The
This work was supported by grants (2016R1A5A1009405 and
2019R1I1A1A01062148) from the National Research Foun-
dation (NRF) of Korea.
Conflict of interest
The authors declare no conflict of interest.
À
undisturbed C C coupling reaction was almost complete after
24 h. In contrast, once the catalyst was removed by filtration,
the reaction stopped, indicating the absence of Pd ions in the
filtrate (Figure 3a). Inductively coupled plasma optical emis-
sion spectrometry (ICP-OES) for Pd content also supported
the absence of Pd in the filtrate, where the detected Pd
content was below the detection limit of the instrument. The
stability and recyclability of heterogeneous catalysts are very
important for practical applications. To evaluate the recycla-
bility of the catalyst, I-5-pSA0.20-Pd0.05 was recovered from the
reaction mixture by centrifugation, and the recovered catalyst
was used in successive runs of the Suzuki–Miyaura cross-
coupling reaction. No decrease in catalytic activity (> 99%
yield) was observed, even after the fifth reaction, thus
indicating the relatively high stability of the catalyst under
Keywords: covalent modification · fragmented ligands ·
heterogeneous catalysis · metal-organic frameworks ·
post-synthetic modification
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