Supramolecular Nanotubules as a Catalytic Regulator for Palladium Cations: Applications in Selective Catalysis

Article abstract of DOI:10.1002/anie.201706373

Despite the recent development of highly efficient and stable metal catalysts, conferral of regulatory characteristics to the catalytic reaction in heterogeneous systems remains a challenge. Novel supramolecular nanotubules were prepared by alternative stacking from trimeric macrocycles, which was found to be able to coordinate with Pd cations. The Pd complexes exhibited a high catalytic performance for C?C coupling reaction. Notably, the tubular catalyst was observed to be controlled by supramolecular reversible assembly and showed superior heterogeneous catalytic activity, which was maintained for a number of cycles or reuse under an aerobic environment. Furthermore, the supramolecular catalyst showed unprecedented selectivity for the multifunctional coupling reaction and was able to serve as a new constructor of asymmetrical compounds.

Full text of DOI:10.1002/anie.201706373

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
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International Edition
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Accepted Article
Title: Supramolecular Nanotubules as Catalytic Regulator for Pd Cation
and Their Application in Selective Catalysis
Authors: Zhegang Huang, Shanshan Wu, Yongguang Li, Siying Xie,
Cong Ma, Joonwon Lim, Jiong Zhao, Dae Seok Kim, Minyong
Yang, Doong Ki Yoon, Myongsoo Lee, and Sang Ouk Kim
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201706373
Angew. Chem. 10.1002/ange.201706373
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10.1002/anie.201706373
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COMMUNICATION
Supramolecular Nanotubules as Catalytic Regulator for Pd Cation
and Their Application in Selective Catalysis
Shanshan Wu,[a],† Yongguang Li,[a],† Siying Xie,[a] Cong Ma,[a] Joonwon Lim,[b] Jiong Zhao,[c] Dae Seok
Kim,[d] Minyong Yang,[d] Doong Ki Yoon,[d] Myongsoo Lee,[e] Sang Ouk Kim,[b]* and Zhegang Huang[a]*
Abstract: Despite recent development of highly efficient and
stable metal catalysts, conferral of regulatory characteristic to the
catalytic reaction in heterogeneous system remains a challenge.
Herein, novel supramolecular nanotubules were prepared by
alternative stacking from trimeric macrocycles, which was found
to be able to coordinate with Pd cations. The Pd complexes
exhibited a high catalytic performance for C-C coupling reaction.
Notably, the tubular catalyst was observed to be controlled by
supramolecular reversible assembly and showed superior
heterogeneous catalytic activity maintained for a number of
recycles or reuse under aerobic environment. Furthermore, the
supramolecular catalyst showed unprecedented selectivity for the
multi-functional coupling reaction and was able to serve as a new
construction of asymmetrical compounds.
ease to handle.21-23 Introduction of a heteroatom such as nitrogen
into conjugated carbon substrates would enhance electron
capacity and thereby bind with metal atoms strongly.24-26 Although
ordered or disordered carbon-supported metal catalysts with
remarkably enhanced activity have been successfully employed,
they still have several deficiencies including lack of long-term
stability, low dispersibility, deactivation or constant leaching, as
well as low recyclability which limit their capacity and applications.
Furthermore, the heterogeneous catalysts could not be controlled
until the reaction is completed because of the difficult separation
between the supporting materials and solvents during the reaction
process, which is not suitable for multi- or selective catalysis.
Developing highly efficient and stable metal catalysts has
attracted great attention in chemistry and material science
because of both economic and environmental reasons.1-4 In
general, metal catalysts with small sizes are preferred due to their
high surface area for efficient catalysis. However, the reversible
reaction of catalysis can result in serious aggregation of metal
species, causing the gradual decrease of the catalytic activity.5-7
For this reason, the stabilizers such as surfactants,8 polymers,9-11
dendrimers,12,13 silica,14,15 and metal oxides16-20 are actively
investigated for preventing metal aggregation. Among them, sp2-
hybridized carbon materials are the most widespread supporting
materials due to their low density, the high surface area and the
Figure 1. (a) Molecular structures of 1 and 2; (b) Schematic representation of
tubular regulator for catalytic reaction based on reversible stacking of
macrocycles.
[a]
[b]
S. Wu, Dr. Y. Li, S. Xie, C. Ma, Prof. Dr. Z. Huang
PCFM and LIFM Lab, School of Chemistry, Sun Yat-sen University,
Guangzhou 510275, PR China
E-mail: huangzhg3@mail.sysu.edu.cn
Dr. J. Lim, Prof. Dr. S. O. Kim
National Creative Research Initiative Center for Multi-Dimensional
Directed Nanoscale Assembly, Department of Materials Science
and Engineering, KAIST, Daejeon 34141, Republic of Korea
E-mail: sangouk@kaist.ac.kr
Aromatic rod amphiphiles consisted of conjugated carbon
and hydrophilic coil segments as the sp2-hybrid carbon family can
aggregate into porous structure to enhance the diffusion of bulky
aryl substrates and the transmission channels are well suitable as
scaffolds for catalytic reaction in separated aromatic space.27-32
Compared with the traditional supporting materials, the
supramolecular substrates can be easily regulated by dynamic
assembly through changing their environments because of their
completely reversible formation.33-36 For example, lateral
attachment of hydrophilic oligoether segments into a linearly
shaped aromatic rod leads the molecules to aggregate into
toroidal nanostructures that are spontaneously connected with
each other to form porous tubules in response to the aromatic
guest.37 The dynamic nature of the aggregates allows them to
adapt the changes of pore surface to be more hydrophobic. As
hinted from the adaptation by dynamic assembly, here we tried to
[c]
[d]
[e]
Prof. Dr. J. Zhao
Department of Applied Physics, The Hong Kong Polytechnic
University，Hung Hom, Kowloon, Hong Kong
D. S. Kim, M. Yang, Prof. Dr. D. K. Yoon
Graduate School of Nanoscience and Technology and KINC,
KAIST, Daejeon, 34141, Republic of Korea
Prof. Dr. M. Lee
State Key Laboratory for Supramolecular Structure and Materials,
College of Chemistry, Jilin University, Changchun 130012, PR
China
†
These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201706373
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align sandwich nanostructures with Pd ions as a catalytic core into
hollow tubes to prepare the supramolecular porous catalyst. The
supramolecular catalyst showed high efficiency for Suzuki-
copper grids and then negatively stained with uranyl acetate, both
the external diameters of the tubules were observed as 5.8 nm
(Figure 2e and S3c). The external diameters of the tubules are
Miyaura (S-M) coupling reaction. Unlike conventional Pd catalysts, identical to those of trimeric macrocycles, suggesting that the
the catalyst could be used as the regulator for metal catalysis
through dynamic assembly (Figure 1). Additionally, the catalyst
recognized the size and type of starting materials and showed
unprecedented selectivity for multi-functional S-M reaction,
having potential to serve as a new concept for asymmetric
catalysis.
tubules originated from the macrocyles stacking. To gain insight
into the packing arrangements of the rod segments within the 1D
aromatic domains, we performed optical experiments. Upon
addition of water into ethanol, both the absorption spectra of 1 and
2 displayed a blue-shifted absorption maximum and reduced
fluorescence intensity compared with those in ethanol solution,
indicating the H-type aggregates were formed from the aromatic
segments (Figure S4).38 Circular dichroism (CD) spectra of the
mixed solution of 1 showed a significant Cotton effect in the
spectral range of the aromatic segments, indicating that the
tubules adopt a one-handed helical structure (Figure 2f). To gain
deeper insight into helical tubules, the atomic force microscopy
(AFM) and two-dimensional X-ray diffraction (2D XRD)
experiments were performed with thin membrane. Figure 3a
shows two kinds of equidistant diffractions were observed at
equator and meridian. The equidistant of 5.2 nm from equatorial
diffractions corresponding to intercolumnar ordering, well
matched with the external diameter determined from TEM
experiments. Meanwhile, along the column axis several periodic
reflections with equidistant of 2.8 nm were observed. Taking into
account the structure and dimensions of trimeric macrocycles,
this diffraction pattern is attributable to a pitch of helical tubules.
Indeed, the AFM image of 1 revealed the formation of a right-
handed helical structure with a pitch of 3.0 nm (Figure 2c), which
is consistent with the CD and XRD results. These observations
indicate that 1 self-assembles into the trimeric macrocycles,
which, in turn, stack on top of each other with mutual rotation to
form the right handed helical tubules.
The catalyst is derived from the self-assembly of a bent-
shaped aromatic amphiphile containing a coordinative unit of
pyridine at the inner position with a alkyl segment at both ends as
hydrophobic segments, which was decorated by hydrophilic
oligoether dendron at its apex (Figure 1). To investigate the
aggregation behavior of bent-shaped molecules, we have
performed vapor pressure osmometry (VPO) experiments. The
molecular weights of 1 based on an octyl-ended chain and 2 with
a tert-butyldimethylsilyloxyl group were calculated 1713 and 1717
D, respectively. However, in the ethanol, the molecular weights of
the primary aggregates were measured to be 5091 and 5212 D,
respectively, which are three-folds as large as a single molecule
(Figure S2), suggesting that both noncovalent macrocycles from
1 and 2 consist of three single molecules.36 Subsequently, the
addition of water into the ethanol solution would drive the trimeric
macrocycles to stack on top of each other to form hollow tubules.
Figure 2a and S3 show micrographs obtained from a 0.02 wt%
mixed solution (EtOH:H2O = 1:3) of 1 and 2 cast onto TEM grids.
The TEM images of both samples show two parallel dark lines
with a uniform distance of 4.0 nm. To further understand the
aggregated nanosturctures, the scanning transmission electron
microscope (STEM) experiment was implemented with a probe
aberration corrector. STEM images show that the 1D objects were
seperated by dark and white segments, indicative of the formation
of hollow tubules with an external diameter of 4.0 nm and a hollow
interior with a diameter of 2.3 nm (Figure 2b and S3). When the
membranes of 1 and 2 were transferred onto carbon-coated
We noticed that the tubular solution of 2 did not show CD
signals within the area of aromatic absorption even though 2
contains chiral side groups (Figure 2f). For investigating the
assembling geometries, we performed AFM measurements of the
sample prepared by drop casting of the solution on a mica
Figure 3. Stacked nanotubules from trimeric marcrocycles. 2D XRD patterns of
1 a) and 2 b) air-dried from mixed ethanol-water dispersions (1/3, v/v, 0.02 wt%).
(Insert: top and front views of oriented neighboring macrocycles) Schematic
representation of the tubules based on helically ordering of 1 c) and alternative
stacking of 2 d). (The yellow balls represent nitrogen atoms, the blue and light
blue chains represent the neighboring alkyl chains and the gray chains
represent alkoxy chains. Alkyl chains in c) and d) are omitted for clarity) Details
please see Figure S5 in supporting information.
Figure 2. TEM, STEM, and AFM images and optical characterizations. TEM a),
STEM b), and AFM c) images of 1 in ethanol-water mixture (1/3, v/v, 0.02 wt%).
d) AFM image of 2 in ethanol-water mixture (1/3, v/v, 0.02 wt%). e) TEM image
stained with uranyl acetate of 1 in ethanol-water mixture (1/3, v/v, 0.02 wt%). f)
Absorption and CD spectra of 1 and 2 in ethanol-water mixture (1/3, v/v, 0.01
wt%).
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10.1002/anie.201706373
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surface. The image clearly revealed that a periodically stacked 1D
object with 6 nm diameter was formed (Figure 2d). The periodic
structure was further analysized by 2D XRD. The 2D image of 2
based on bulky alkyl segments displays sharp spots in same
direction that correspond to equidistant q-spacings which indexed
as 0.9 nm (Figure 3b). Given the interdistance from macrocycle
stacking (0.45 nm), the space of 0.9 nm is approximately twice
larger than that between neighboring cycles, suggesting the
formation of non-chiral tubules with an alternatively cyclical
stacking (Figure 3d). In contrast to 1, there is large steric
hindrance in the inside of trimeric macrocycles prepared from 2.
So the neighboring macrocycles stacked on each other without
overlay of the bulky hydrophobic segments to reduce the contact
between aromatic segments and solvents.
Owing to the periodical location of pyridine at the inner
surface of the tubules, it is facilitative for Pd cation to coordinate
with pyridine resulting in the formation of the supramolecular
catalyst. The dispersion of Pd within self-assembled tubules
displayed enhanced stability than dissolved state due to the
sandwich structure (Figure S6). In mixed solution with PdCl2, the
Pd cation was successfully coordinated to the pyridine ligand with
the observation of the red-shifted absorption band and
significantly suppressed emission intensity (Figure S7a and b). To
take insight into the formation of supramolecular catalyst, X-ray
photoelectron spectra (XPS) experiments were further performed.
In the high-resolution spectra, a peak at 399.3 eV was observed
and assigned to the pyridine nitrogen (1s).39 However, the peak
positively shifted to 400.1 eV in the supramolecular catalyst,
confirming the existence of interaction between nitrogen and Pd
(Figure S7c).40 The amount of Pd in tubules was determined by
inductively coupled plasma atomic emission spectroscopy (ICP-
AES), showing 92% of PdCl2 formed the complexes on the inner
pore of tubules. The molar ratio of nitrogen to palladium within the
nanotubule was observed as 2.4 : 1 by semi-quantitative
calculation from XPS experiments, which indicates Pd cation is
coordinated by alternatively stacked pyridine (Figure 1).
Owing to the highly ordered porous structure and the
significant stability for Pd cation at the porous walls, the Pd-
coordinated tubule of 2 can be used as supramolecular catalysts
with high active capacity for the S-M reaction with phenylboronic
acid at ambient temperature. The tubular catalyst of 2 gave high
catalytic conversions for all benzene halide (Table S1, entries 1-
3). With bulky substrates, however, the catalyst did not work as
biphenyl substrates (Table S1, entry 4). The results showed that
biphenyl halide in this reaction was larger than the aperture of the
tubules and the reaction could only occur for small benzene
substrate. Notably, the tubular catalyst exhibited the switching
behavior according to reversible self-assembly, hence this
supramolecular catalyst has served as the regulator for metal
catalyst. As a result of poor diffusion of the reagents in molecularly
dissolved state, the reaction could be halted immediately after the
addition of ethanol to the reaction mixture leading to the
deaggregation of the tubules, which induces the loss of catalytic
activity. Thus, the conversion could also be monitored freely after
the reaction was quenched. Figure S8 shows the conversion in
real time, demonstrating the catalytic reaction undergoes within
10 min with high conversion. Furthermore, the supramolecular
catalyst exhibited high reusability under the reaction conditions
with an aryl halide/molecule 2 molar ratio of 50:1. After completion
of the reaction, the dissolved macrocycles were readily recovered
by centrifugation. The catalyst was reformed after the addition of
water and reused upon new reactants were added. After recycling
procedures, we removed the catalyst and analyzed the reaction
mixture by ICP-AES. No leaching Pd was detected during the
disassembly and assembly processes, and the initial activity was
completely maintained during five cycles of the reaction (Figure
S9). AFM and TEM studies clearly revealed that the reassembled
tubules of 2 remains with same size and morphology even after
exposure to the coupling reaction. Based on these results, we
conclude that the tubular catalyst of
2 exhibits superior
heterogeneous catalytic activity in terms of stability, recyclability,
and reusability in C-C coupling reaction. In contrast to general Pd
nanoparticles on solid supports, the catalyst additionally shows
regulatory characteristic in heterogeneous reaction by
supramolecular assembly and dis-assembly process.5,10
The special regulation with uniform porous surface motivated
us to explore the selectivity of the S-M reaction using multi-
functional substrate to develop new asymmetric coupling reaction.
Thus, the reaction with bi-reactive sites was investigated with 4-
bromophenylboronic acid and bromobenzene. It is known that the
general Pd catalysts usually give aryl polymers or multiple
products (Table S1, entry 5). Remarkably, when the reaction was
carried out by using tubular catalyst of 2, the product of 4-
bromobiphenyl was obtained reaching up to 90 % within 30 min
(Table S1, entry 6). The probable reason for the high selectivity
can be explained by spatial effect of tubular pores. As mentioned
above, the aperture of tubular substrate is suitable for small
benzene bromide, thus resulting in the enhanced activity for
monocoupling reaction.
In summary, we have demonstrated that stimuli-responsive
supramolecular tubules through the self-assembly of trimeric-
macrocycles with alternative stacking can be used as catalytic
regulator in heterogeneous system. The porous tubules from the
self-assembly of N-substituted aromatic macrocycles provide a
unique property to stabilize Pd cation on the inner surface against
metal agglomeration, and provide high catalytic activities during a
number of recycles owing to its special sandwich construction for
the stable formation of coordinated bond with Pd cation. Notably,
the heterogeneous catalyst based on the self-assembled tubular
substrate could be suspended and restarted conveniently through
the supramolecular reversible assembly. Furthermore, the
catalyst was endued with unprecedented selectivity within aryl
polymerization due to the spatial effect of tubular aperture. The
special regulation with unprecedented selectivity for C-C reaction
presented here would provide a useful way to construct
asymmetrical compounds with high catalytic activity.
Acknowledgements
This work was supported by Sun Yat-sen University, the NSFC
(21302030), (21503284), Guangzhou Science and Technology
Program (201707010248), the Key Laboratory of Functional
Inorganic Material Chemistry (Heilongjiang University), Ministry of
Education (2013kf05), and the Open Project of State Key
Laboratory of Supramolecular Structure and Materials
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Entry for the Table of Contents
COMMUNICATION
Supramolecular Catalystic Regulator
S. Wu, Y. Li, S. Xie, C. Ma, J. Lim, J.
Zhao, D. S. Kim, M. Yang, D. K. Yoon,
M. Lee, S. O. Kim,* Z. Huang*
Page No. – Page No.
Nanotubules as catalytic regulator: A novel supramolecular catalyst was
prepared by alignment of sandwich nanostructures with metal catalytic core. The
catalyst could be used as the regulator for metal catalysis through reversible
assembly (see picture).
Supramolecular Nanotubules as
Catalytic Regulator for Pd Cation and
Their Application in Selective
Catalysis
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