Postsynthetic Metalation of a Robust Hydrogen-Bonded Organic Framework for Heterogeneous Catalysis

Article abstract of DOI:10.1021/jacs.9b03766

Hydrogen-bonded organic framework (HOF)-based catalysts still remain unreported thus far due to their relatively weak stability. In the present work, a robust porous HOF (HOF-19) with a Brunauer-Emmett-Teller surface area of 685 m² g^-1 was reticulated from a cagelike building block, amino-substituted bis(tetraoxacalix[2]arene[2]triazine), depending on the hydrogen bonding with the help of π-πinteractions. The postsynthetic metalation of HOF-19 with palladium acetate afforded a palladium(II)-containing heterogeneous catalyst with porous hydrogen-bonded structure retained, which exhibits excellent catalytic performance for the Suzuki-Miyaura coupling reaction with the high isolation yields (96-98%), prominent stability, and good selectivity. More importantly, by simple recrystallization, the catalytic activity of deactivated species can be recovered from the isolation yield 46% to 92% for 4-bromobenzonitrile conversion at the same conditions, revealing the great application potentials of HOF-based catalysts.

Full text of DOI:10.1021/jacs.9b03766

Communication
Cite This: J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
pubs.acs.org/JACS
Postsynthetic Metalation of a Robust Hydrogen-Bonded Organic
Framework for Heterogeneous Catalysis
Bin Han, Hailong Wang,* Chiming Wang, Hui Wu, Wei Zhou,§ Banglin Chen,*,‡
†
,†
†
§
,
†
and Jianzhuang Jiang*
†Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry,
University of Science and Technology Beijing, Beijing 100083, China
‡
Department of Chemistry, University of Texas at San Antonio, San Antonio, Texas 78249-0698, United States
§
Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, United States
*
S Supporting Information
additional π−π interactions would significantly enhance the
ABSTRACT: Hydrogen-bonded organic framework
HOF)-based catalysts still remain unreported thus far
due to their relatively weak stability. In the present work, a
stability when aromatic building blocks are employed for
5
g,6f
(
constructing HOFs,
rendering it possible to fabricate
heterogeneous catalysts with robust frameworks as the porous
support of homogeneous species. In particular, the excellent
recyclability of HOFs through simple recrystallization enables
them to be regenerated easily, thus endowing the sustainable
advantage to HOF-based catalysts.
robust porous HOF (HOF-19) with a Brunauer−
2
−1
Emmett−Teller surface area of 685 m g was reticulated
from a cagelike building block, amino-substituted bis-
(
tetraoxacalix[2]arene[2]triazine), depending on the
hydrogen bonding with the help of π−π interactions.
The postsynthetic metalation of HOF-19 with palladium
acetate afforded a palladium(II)-containing heterogeneous
catalyst with porous hydrogen-bonded structure retained,
which exhibits excellent catalytic performance for the
Suzuki−Miyaura coupling reaction with the high isolation
yields (96−98%), prominent stability, and good selectiv-
ity. More importantly, by simple recrystallization, the
catalytic activity of deactivated species can be recovered
from the isolation yield 46% to 92% for 4-bromobenzoni-
trile conversion at the same conditions, revealing the great
application potentials of HOF-based catalysts.
Herein, a novel organic cage of amino-substituted bis-
tetraoxacalix[2]arene[2]triazine) (L) composed of five six-
(
membered aromatic rings has been designed and prepared as a
building block for assembling HOFs (Figure 1a and Scheme S1,
Supporting Information). Depending on the hydrogen bonding
between neighboring building blocks with the help of rich π−π
interactions between intercage aromatic moieties, the first cage-
eterogeneous catalysis plays a dominant role in the
1
H
chemical and pharmaceutical industry. As a result,
continuous efforts have been paid toward developing effective
methods for synthesizing heterogeneous catalysts with high
efficiency and in particular with an easy recovery and recycling
nature. In the past several years, by immobilizing homogeneous
2
catalysts inside the porous supports such as zeolites, metal−
3
organic frameworks (MOFs), and covalent organic frameworks
4
(
COFs), diverse heterogeneous catalysts with boosted activity
and stability have been fabricated. However, the regeneration of
these heterogeneous catalysts is still challenging due to their
nonrenewable porous supports.
In the same way as MOFs and COFs, porous hydrogen-
Figure 1. Crystal structure of HOF-19 showing (a) molecular organic
cage L; (b) hydrogen bonding ribbon comprising neighboring AT
groups; (c, d) two kinds of intercage cofacial π−π interactions; (e) the
C−H···π interaction; and (f) a packing diagram of HOF-19 showing the
bonded organic frameworks (HOFs) are self-assembled from
5
discrete molecular modules as well. Despite the outstanding
6
properties of HOFs revealed in the fields of gas storage, small-
7
8
9
1
D channel surfaces highlighted as yellow/gray (inner/outer) curved
molecule separation, sensing, and proton conduction, reports
over HOF-based catalysts still remain unknown, to the best of
our knowledge, due to the relatively poor stability associated
with the weak hydrogen bonding connection between discrete
planes (C, slight cyan; O, pink; N, blue; H, white).
Received: April 8, 2019
5
−9
building blocks in HOFs.
Fortunately, the introduction of
©
XXXX American Chemical Society
A
DOI: 10.1021/jacs.9b03766
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX

Journal of the American Chemical Society
Communication
based HOF (HOF-19) is constructed, and its hydrogen-bonded
structure is clearly revealed by single-crystal X-ray diffraction
analysis. The N sorption measurement at 77 K discloses a
2
2
−1
Brunauer−Emmett−Teller (BET) surface area of 685 m g for
activated HOF-19. Postfunctionalization of this HOF with
palladium acetate gives a palladium(II)-containing HOF-
1
9⊃Pd(II) with parent hydrogen-bonded structure maintained
according to the powder X-ray diffraction (PXRD) analysis,
indicating the robustness of HOF-19. Further evidence on the
robustness of HOF-19 comes from the excellent stability and
recyclability of HOF-19⊃Pd(II) in p-xylene in the presence of
potassium carbonate at 150 °C. Under such experimental
conditions, the Suzuki−Miyaura coupling reaction is able to be
selectively promoted in high isolation yields (96−98%),
revealing the predominant catalytic activity of HOF-based
materials for the first time. Nevertheless, the catalytic activity of
deactivated species, with the 46% isolation yield for the
conversion of 4-bromobenzonitrile, is recovered to 92% by
simple recrystallization regeneration, revealing the great
application potentials of HOF-based catalysts.
Figure 2. N
sorption isotherms of HOF-19a (black) and HOF-
2
1
9⊃Pd(II) (blue) at 77 K (solid symbols, adsorption; open symbols,
desorption).
well with the simulated one for HOF-19 in Figure S6
(
Supporting Information), indicating the hydrogen-bonded
A facile reaction between chloride-substituted bis-
tetraoxacalix[2]arene[2]triazine) and ammonium hydroxide
structure retained by the post-treated species and illustrating
the HOF robustness again. Inductively coupled plasma (ICP)
analysis gives a Pd content of 3.8 wt % included in HOF-
10
(
afforded L (Scheme S1 and Figures S1 and S2, Supporting
Information). The slow evaporation of the formic acid solution
of L gave single crystals of HOF-19 with poor solubility in
common organic solvents (except only DMSO). Single-crystal
X-ray diffraction data confirms the three-dimensional (3D)
porous structure of HOF-19 (Figure 1; Tables S1 and S2,
Supporting Information). As exhibited in Figure 1, depending
on the multiple N−H···N hydrogen bonding between intercage
1
9⊃Pd(II). In the X-ray photoelectron spectrum shown in
Figure S7 (Supporting Information), the observation of two
peaks with the binding energy of 338.1 and 343.4 eV
corresponding to Pd 3d5/2 and Pd 3d3/2, respectively, confirms
divalent palladium ions bound by HOF-19. The slight down-
shift of Pd 3d5/2 and Pd 3d3/2 binding energy for HOF-
1
9⊃Pd(II) relative to that (338.3 and 343.6 eV) of palladium
2+
2
-aminotriazinyl (AT) groups with the help of π−π interactions
acetate indicates the presence of an interaction between Pd
12
from intercage benzene moieties, two-dimensional porous
hydrogen-bonded supramolecular structures containing one-
dimensional (1D) channels with the size of 8.0 × 13.6 Å along
the [010] direction are formed, which are further packed into
the 3D architecture of HOF-19 depending on the intercage
cofacial π−π interaction between AT groups and C−H···π
interaction (actually a kind of π−π interaction). The PLATON
calculation discloses 47% void space for HOF-19, which
should be favorable for the molecular substrate diffusion.
The bulk material of HOF-19 with good thermal stability was
obtained by diffusing acetone into the formic acid solution of L
ions and HOF-19. The slight upshift for the binding energy of
the amino group of HOF-19 after including palladium acetate
2
+
not only indicates HOF-19 interacting with Pd ions but also
suggests the amino groups, instead of the intracage cavity, as
active sites to bind the metal ions (Figure S8, Supporting
Information). The energy-dispersive spectroscopy (EDS)
mapping of HOF-19⊃Pd(II) clearly hints at the homogeneous
distribution of the Pd element, excluding the presence of Pd
nanoparticles (Figure S9, Supporting Information). After
postmodification with Pd(OAc)2 to give HOF-19⊃Pd(II)
with palladium ions decorated on the surface of HOF channels,
11
2
−1
(
1
1
Figure S3, Supporting Information). Acetone-exchanged HOF-
9 was degassed at 25 °C to give an activated sample (HOF-
9a). The PXRD pattern of HOF-19a is well consistent with the
the BET surface area was decreased to 159 m g , indicating the
partial structural collapse of HOF after Pd inclusion.
2
+
To illustrate the proof-of-concept of the HOF-based catalyst,
the Suzuki−Miyaura coupling reaction was selected as a model
reaction to examine the catalytic activity of HOF-19⊃Pd(II). As
can be found in Table 1, in the presence of 0.260 mmol % HOF-
19⊃Pd(II), the halogenated benzene substrates (entries 1−6)
were successfully transformed to corresponding coupling
products in the high isolation yields of 96−98% within a short
time of 1.5−2.5 h. In particular, for the conversion of 1-bromo-4-
nitrobenzene, only about 0.260% Pd content in HOF-19⊃Pd-
(II) was revealed to be leached into the filtrate according to the
ICP measurement, indicating the strong interaction between
simulated profile of HOF-19 (Figures S4 and S5, Supporting
Information), indicating its robust nature. The N sorption
2
measurement at 77 K reveals its type I adsorption curve with a
3
−1
N uptake of 287 cm g at 1.0 bar (Figure 2). The experimental
2
3
−1
pore volume of 0.45 cm g is well consistent with the
theoretical value (0.48 cm g ; Table S1). The BET surface
area of HOF-19a was calculated to be 685 m g .
3
−1
11
2
−1
The multiple hydrogen bonding and π−π interactions
between neighboring cages enhance the robustness of HOF-
1
9. The poor solubility of HOF-19 in common organic solvents
2
+
could effectively stabilize the framework in solution. In addition,
abundant triazinyl nitrogen atoms and amino groups inside the
pores of HOF-19 provide enough binding sites to incorporate
catalytically active metal ions. All these characteristics inspire us
to fabricate a heterogeneous catalyst with HOF-19 as the porous
support. The immersion of activated HOF in an acetone
solution of palladium acetate (0.100 mM) afforded palladium-
Pd and HOF-19. Under the same conditions, the catalytic
activity of 0.260 mmol % HOF-19⊃Pd(II) is even comparable
to the excellent performance of 0.500 mmol % COF-LZU1⊃Pd-
(II) catalyst toward the reaction of 1-bromo-4-methoxybenzene
12
with phenylboronic acid, indicating the excellent catalytic
activity of HOF-19⊃Pd(II) (Table 1). Nevertheless, HOF-
19⊃Pd(II) shows a much higher catalytic efficiency in
comparison with palladium acetate, a mixture of HOF-19 and
(
II)-containing HOF-19⊃Pd(II). Its PXRD pattern matches
B
DOI: 10.1021/jacs.9b03766
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX

Journal of the American Chemical Society
Communication
Table 1. Catalytic Performance of HOF-19⊃Pd(II) Catalyst
recrystallization, exhibiting almost recovered activity. These
results reveal the great application potentials of HOF-based
catalysts. We hope the present result will ignite more research
interest toward exploration of HOF-based catalysts and other
applications.
a
in the Suzuki−Miyaura Coupling Reaction
b
entry
R
X
time (h)
yield (%)
1
2
3
4
5
6
7
8
−CHO
−CN
−H
Br
Br
Br
Br
Br
I
Br
Br
Br
Br
Br
Br
Br
Br
2.5
1.5
2.0
2.5
2.0
1.5
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
97
97
98
97
96
97
19
13
96
71
70
∼7
69
58
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/jacs.9b03766.
■
*
S
−NO2
−OMe
−OMe
−Ph
−PhOMe
−OMe
−OMe
−OMe
−OMe
−Ph
Experimental details, NMR spectra, TGA curve, SEM
photos, PXRD patterns, XPS spectra, EDS mapping of
HOF-19 and/or HOF-19⊃Pd(II) (PDF)
Crystallographic data for HOF-19 (CIF)
c
9
d
10
11
12
13
14
AUTHOR INFORMATION
Corresponding Authors
*hlwang@ustb.edu.cn
*banglin.chen@utsa.edu
*jianzhaung@ustb.edu.cn
ORCID
Hui Wu: 0000-0003-0296-5204
Wei Zhou: 0000-0002-5461-3617
Banglin Chen: 0000-0001-8707-8115
Jianzhuang Jiang: 0000-0002-4263-9211
e
■
f
d
d
−PhOMe
a
Reaction conditions: aryl halide (1.00 mmol), phenylboronic acid
1.50 mmol), K CO (2.00 mmol), HOF-19⊃Pd(II) (7.5 mg, 0.260
mmol %), p-xylene (4 mL), 150 °C. Isolation yield. 0.500 mmol %
COF-LZU1⊃Pd(II).
Pd(OAc) and HOF-19 (7.5 mg). 0.260 mmol % Pd/C (10 wt %).
(
2
3
b
c
11
d
e
0.260 mmol % Pd(OAc) . 0.260 mmol %
2
f
2
palladium acetate, and Pd/C catalyst, confirming the crucial role
of palladium(II) ions deposited on the channel surfaces of HOF-
9 on the present heterogeneous catalysis of the Suzuki−
Miyaura coupling reaction. Interestingly, under the same
reaction conditions, the substrates of 4′-bromo-1,1′-biphenyl
and 4-methoxy-4′-bromo-1,1′-biphenyl with large molecular
size of 7.5 × 13.9 and 7.5 × 16.0 Å, respectively, were converted
into the corresponding product only with the isolation yield
below 20% even after 4.0 h, which are even much lower than
Notes
The authors declare no competing financial interest.
1
ACKNOWLEDGMENTS
■
Financial support from the Natural Science Foundation of
China (21631003 and 21805005), the Fundamental Research
Funds for the Central Universities (FRF-BD-17-016A), Welch
Foundation (AX-1730), National Science Foundation (DMR-
606826), and University of Science and Technology Beijing is
gratefully acknowledged.
1
those with Pd(OAc) as the catalyst (Table 1 and Table S3,
Supporting Information), indicating the presence of pore size
selectivity of the HOF-19⊃Pd(II) catalyst.
2
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■
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four cycles of reaction, indicating again the good stability of the
HOF-based catalyst (Figures S6 and S10, Supporting
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