Woven Polymer Networks via the Topological Transformation of a [2]Catenane

Article abstract of DOI:10.1021/jacs.0c06416

Weaving technology has been widely used to manufacture macroscopic fabrics to meet the artistic and practical needs of humanity for thousands of years. However, the fabrication of molecular fabrics with fascinating topologies and unique mechanical propert

Full text of DOI:10.1021/jacs.0c06416

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Article
Woven Polymer Networks via the Topological Transformation of A [2]Catenane
Guangfeng Li, Lei Wang, Liang Wu, Zhewen Guo, Jun Zhao, Yuhang Liu, Ruixue Bai, and Xuzhou Yan
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c06416 • Publication Date (Web): 29 Jul 2020
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Woven Polymer Networks via the Topological Transformation of A
[2]Catenane
Guangfeng Li,⊥ Lei Wang,⊥ Liang Wu,⊥ Zhewen Guo, Jun Zhao, Yuhang Liu, Ruixue Bai, and Xuzhou
Yan*
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School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao
Tong University, Shanghai 200240, P. R. China
ABSTRACT: Weaving technology has been widely used to manufacture macroscopic fabrics to meet the artistic and practical needs
of humanity for thousands of years. However, the fabrication of molecular fabrics with fascinating topologies and unique mechanical
properties represents a significant challenge. Herein, we describe a topological transformation strategy to construct woven polymer
networks (WPNs) at the molecular level via ring-opening metathesis polymerization (ROMP) of a zinc-template [2]catenane. The
key feature of this approach is the exploitation of the preexisted catenane crossing points that maintain the dense woven structure,
and the flexible alkyl chains on the [2]catenane that synergistically work with the crossing points to modulate the physicochemical
and mechanical properties of the woven materials. As a result, the WPN possesses a certain degree of flexibility and stretchability,
as well as high thermostability and mechanical robustness. Furthermore, we could remove the zinc ions to endow the WPN with more
degrees of freedom and then enhance its mechanical behaviors by remetalation. This study not only provides a novel strategy towards
woven materials with intriguing structural features and emergent mechanical adaptivities, but also highlights that mechanically inter-
locked molecules could offer unique opportunities for the construction of smart supramolecular materials with peculiar interlaced
topologies at the molecular scale.
nal studies stand for a significant advancement towards con-
structing woven structures at the molecular level. However, ra-
tional and efficient synthesis methods remain very rare, espe-
cially for the preparation of flexible woven materials analogous
to the macroscopic fabrics.
Introduction
As one of the oldest and most unfailing technologies in hu-
man history, weaving has a great influence over our daily lives
and production,1,2 and in a sense, is closely related to the ad-
vancement of human civilization. The synergy of highly direc-
tional warp and weft threads in the weaving forms can generate
fabrics with unique topologies as well as greatly enhanced me-
chanical properties and dynamics compared to their original
materials.3,4 Inspired by the artistry and practicality of artificial
fabrics, weaving molecules into patterns resembling those of
macroscopic fabrics has been a long-standing pursuit of chem-
ists.5 However, the realization of weaving at the molecular level
for the construction of atomically defined woven structures pre-
sents a significant challenge, possibly owing to the lack of pow-
erful methodology to direct molecular threads to cross at regular
intervals mutually.
Mechanically interlocked molecules (MIMs),9,10 for example,
rotaxanes11-13 and catenanes,14-16 are topological structures that
are held together through mechanical bonds, which have found
broad applications in various fields spanning from synthetic
chemistry17-23 to materials science24-32 and nanotechnology.33-34
When it comes to constructing woven topological structures,
catenane molecules are also promising because of the following
advantages: (i) Catenanes possess innate crossover geometries
that could facilitate the formation of interwoven threads when
suitable weaving strategies are employed; (ii) Versatile homo-
or heterogeneous ring-like components of the catenanes are able
to enrich the library of woven topological structures; (iii) Non-
covalent crossing points in catenanes would allow the threads
to slide in respect to each other while preserving the interlaced
nature, thereby empowering reversible control over the me-
chanical behaviors of the woven materials. As such, we envi-
sion that catenanes can be a powerful and versatile platform for
the design and preparation of mechanically adaptive materials
with woven patterns that are hardly attainable via the crystal
engineering methods. Nevertheless, undoing the mechanical
bonds of catenanes to construct extended woven materials has
remained unexploited.
In 2016, Yaghi et al. reported an ingenious metal-template
strategy to make the first woven covalent-organic framework
(COF), wherein the Cu(I) centers could be reversibly removed
to manifest the tunable mechanical and dynamic properties of
the materials.6 Whereafter, sacrificial metal-organic frame-
works (MOFs) were well designed by Wang and co-workers to
enable the formation of 2D conjugated sheets with interwoven
patterns.7 A year later, the Wennemers group discovered the
first triaxial woven superstructure, which demonstrated the
markedly augmented robustness compared with the non-woven
construct made of the same organic components.8 These semi-
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Figure 1. (a) Cartoon representation of an olefin-containing [2]catenane. (b) The mechanism for the formation of 3D WPNs via the ROMP
of the [2]catenane. The cartoon of the [2]catenane represents the E,E isomer. (c) Cartoon representation of the 3D WPN.
Herein, we report a topological transformation strategy for
the design and synthesis of woven polymer networks (WPNs)
via ring-opening metathesis polymerization (ROMP) of a
[2]catenane (Figure 1). The resultant 3D WPN consists of rigid
metal-coordinated crossing points and flexible alkyl chains. The
hybrid structural characteristic confers the WPN with flexible,
ductile yet robust features, reminiscent of macroscopic fabrics.
Specifically, we firstly synthesized an olefin-containing [2]cat-
enane by the combination of metal-coordination and ring-clos-
ing metathesis. Subsequently, the highly efficient ROMP was
employed as the tool to open the double bonds of the [2]cate-
nane and then splice them together to form an extended polymer
network, in which the crossing points remain intact. Further-
more, we could reversibly remove and add the metal ions in the
centers of the crossing points to tune the properties of the WPNs.
the network propagation stage until polymerization finishes, as
indicated by the appearance of large amounts of precipitates.
Finally, we intentionally quenched the reaction with several
drops of ethyl vinyl ether. Notably, the metal-coordinated units
maintain their crossover geometries during ROMP as we have
seen in the RCM for the [2]catenane preparation and other
ROMP systems,37,38 thus leading to the generation of the ex-
tended WPN (Figure 1c).
To demonstrate the topological transformation of the soluble
[2]catenane into the extended insoluble WPN, we first per-
formed 13C cross-polarization with magic-angle spinning
(CP/MAS) solid-state NMR experiments. In the spectra of the
[2]catenane and WPN, we observed that the characteristic peaks
on the [2]catenane are well retained in the WPN (Figure 2a).
Besides, the peaks corresponding to the WPN broaden com-
pared with the ones on the [2]catenane upon ROMP, indicative
of the existence of extended structure in the WPN. Furthermore,
Fourier-transform infrared (FT-IR) spectrum of the WPN show-
cases that signal at 1612 cm−1 is consistent with that of the
[2]catenane precursor, which is corresponding to the C=N
stretching mode for imine bonds (Figure S15). These observa-
tions confirm that the metal-coordinated crossing points were
preserved in the WPN.
Results and discussion
We adopted the ring-closing metathesis (RCM) of the
tetraolefin complex (ZnBIP2) composed of two benzylic 2,6-
diiminopyridine (BIP) ligands and one Zn(II) center to synthe-
size a [2]catenane with two identical macrocyclic alkenes
(Scheme S1 and Figure 1a).35 Subsequently, the 3D WPN was
obtained via the ROMP of the [2]catenane, which was initiated
by the second-generation Grubbs catalyst. The mechanism for
the formation of the WPN is shown in Figure 1b.36 Initiation
starts with the coordination of the ruthenium alkylidene com-
plex to the olefin units on the [2]catenane monomer. Four-mem-
bered metallacyclobutane complexes are then formed by the
[2+2]-cycloaddition at both sides of the [2]catenane, which rep-
resents the beginning of the growing polymer network. Further-
more, the coordination complexes are able to undergo a cy-
cloreversion reaction to generate new ruthenium alkylidene
centers on the [2]catenane. The same steps are repeated during
Serendipitously, we found that the interlaced Schiff-base co-
ordination complex ZnBIP2 is a fluorophore, which has aggre-
gation-induced emission (AIE) characteristics,39-46 as suggested
by the gradually enhanced emission upon aggregation in
CH2Cl2/hexane mixtures (Figures S18 and S19). Therefore, we
anticipate that the AIE phenomenon could serve as an efficient
probe to monitor the topological transformations from the
tetraolefin ZnBIP2 to the discrete [2]catenane and then to the
infinite WPN. As shown in Figure 2b, the solid state emission
intensity of the tetraolefin ZnBIP2 was lowered by nearly three
quarters after formation of its double macrocyclization product
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Figure 2. (a) Partial 13C CP/MAS solid state NMR (125 MHz, 298 K) of the [2]catenane and WPN. (b) Fluorescence emission and (c)
normalized spectra of the complex ZnBIP2, [2]catenane and WPN in the solid state (λex = 380 nm). (d) XRD patterns of the [2]catenane and
WPN. (e) TGA curves of the [2]catenane and WPN recorded under N2 flow (50 mL min−1) with a heating rate of 20 °C min−1. (f) Normalized
swelling curves of the WPN in different solvents. (g) Swelling ratio of the WPN in DCM. DCM = dichloromethane, THF = tetrahydrofuran,
DMF = dimethyl formamide.
of the [2]catenane. At the same time, the formation of the [2]cat-
enane was also accompanied by a ~43 nm red-shift of the max-
imum emission wavelength (Figure 2c). The differences of the
emissive behaviors between the tetraolefin complex ZnBIP2 and
the ring-closed [2]catenane imply that the interlaced fluoro-
phore would exhibit different photophysical properties in dif-
ferent topological structures, as considered from the molecular
conformation and the extent of molecular aggregation in the
solid state. Before ring-closing metathesis, the fluorophore is
relatively flexible and less restricted so that it can aggregate
tightly in the solid state and result in strong emission. After the
formation of the [2]catenane, the more stereoscopic mechani-
cally interlocked structure imposes more restrictions on the ag-
gregation of the fluorophore part and thus lowers its emission.
Moreover, it was reported that the benzylic groups of each cycle
prefer to interact with the 2,6-diiminopyridine groups of the
other interlocked ring via π-π stacking in a parallel arrange-
ment,35 which are thought to be accounted for the observed red-
shift of the maximum emission wavelength on the [2]catenane.
Upon ROMP, the conformation and geometry of the fluoro-
phore in the WPN tend to return to the modes in the tetraolefin
ZnBIP2, and thus result in the enhanced emission intensity and
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blue-shifted maximum emission wavelength (~12 nm) (Figure
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hexane, while it swelled immediately and reached the maxi-
mum swelling ratios quickly (~300 s) in the other five solvents
(Figure 2f). For example, the swelling ratio of the WPN in di-
chloromethane (DCM) is only 170% (Figure 2g). Combined
with the aforementioned results, it is thus reasonable to conjec-
ture that the low swellability of the WPN can be attributed to
the dense interlaced structure, which suppresses the movement
and expansion of the flexible chains inside the network.47
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2b and c). The incomplete recovery of the light-emitting prop-
erties is understandable on account of the restriction of the
fluorophores in the dense WPN. The explanations were further
supported by the measurement of the quantum yields of the
three structures (9.99% for the ZnBIP2, 4.76% for the [2]cate-
nane, and 8.97% for the WPN), which showed similar variation
trend along with the structural transformations (Figure S22).
The unique photophysical properties of the fluorophore corrob-
orate that the crossing points were well preserved in different
structures during the topological transformations, suggestive of
the woven nature of the extended network formed via the
ROMP of the [2]catenane.
To gain a deeper insight into the topological transformation
process and the resultant woven structure of the WPN at the
molecular level, we carried out coarse-grained (CG) molecular
simulation. The detailed modelling of the ROMP process of the
[2]catenane is computationally challenging and limits accessi-
ble time and space scales which are far below those needed to
observe the process. Instead, the CG model of the ZnBIP2 used
here could also provide a qualitative yet valuable approach to
evaluate the structure of WPN at the CG level. In terms of the
size of the complex ZnBIP2, an idealized CG molecular model
was developed, in which the structural features of the complex
are well retained in CG model and the patchy bead is used to
mimic the bonding between two monomers (Figure 3a). The
particle-particle interactions are strictly repulsive by Weeks-
Chandler-Anderson potential while the patchy beads are inter-
acted by shifted Lennard-Jones potential at 2ꢀ. The CG simu-
lation was performed using a simulation box containing 600
ZnBIP2 molecules by Langevin dynamics using LAMMPS
code48 and the configuration was visualized by VMD soft-
ware.49 The resulting equilibrium configuration clearly exhibits
the formation of WPN at a large spatial scale while a very small
fraction of the ZnBIP2 is seen to be non-bonded (Figure 3b).
The structure of the WPN can be described by site-site radial
distribution function (RDF) ꢁ(ꢂ) (Figure 3c). The very high
peak of the patchy-patchy RDF at ꢂ = 0.2ꢀ is the sign of bond-
ing between two monomers. The peak of Zn-Zn RDF at ꢂ =
10ꢀ exhibits the most of CG ZnBIP2 forms WPN in equilibrium
and the peaks around at ꢂ~20ꢀ are related to the minor cate-
nated patterns in the system (Figure 3d).
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Figure 3. (a) Coarse-grained (CG) molecular model of the ZnBIP2
and the gray particles represent patchy beads. (b) Equilibrium con-
figurations of the CG model of the WPN. (c) Radial distribution
functions of the Zn atoms and patchy particles in the WPN. (d)
Typical topological structures of the WPN in the equilibrium state.
After confirming the woven patterns in the polymeric net-
work, we ulteriorly examined the physicochemical properties of
the WPN. The X-ray diffraction (XRD) experiments were per-
formed to study the crystallinity of the [2]catenane and WPN.
The XRD patterns show that the crystallinity of the [2]catenane
was not retained in the WPN (Figure 2d). We speculate that the
amorphous phase of the extended network originates from the
coexistence of rigid crossing points and flexible alkyl chains in
the WPN. In fact, the hybrid structural feature would be benefi-
cial for the mechanical adaptivity of the woven materials. Fur-
thermore, we found that the lack of crystallinity shows no effect
on the thermal performance of the WPN. Thermogravimetric
analyses (TGA) display that the 5% weight losses of the [2]cat-
enane and WPN are at about 215 and 320 °C (Figure 2e), re-
spectively, suggesting the improved thermal stability via mo-
lecular weaving.
We then performed swelling tests of the WPN in six solvents
of different polarities to gain a deeper understanding of the pe-
culiar network structure. The WPN didn’t swell in nonpolar n-
Figure 4. (a) Storage modulus (E′) and loss modulus (E″) versus
oscillation stress of the WPN (frequency = 1.0 Hz, 298 K). (b) E′
and E″ versus frequency of the WPN (strain amplitude = 0.1%, 298
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K). (c) E′ and E″ versus temperature of the WPN (strain amplitude
= 0.6%, frequency = 1.0 Hz). (d) Stress-strain curve of the WPN
with a deformation rate of 5.0 mm min−1.
inductively coupled plasma (ICP) analysis. Furthermore, the
material can be remetalated with Zn(II) ions by soaking in a
CH3OH solution of ZnClO4⋅6H2O, and the ICP analysis shows
that ~93% of Zn(II) ions were restored. In the 13C CP/MAS
solid state NMR spectra, the peaks corresponding to the aro-
matic carbon atoms were maintained, suggesting that the WPNs
before and after demetalation are chemically stable (Figure
S13).
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Upon establishing the woven pattern of the WPN by various
experimental and theoretical results, we proceed to investigate
how the woven structure inside the network influences its me-
chanical performance. The thermomechanical properties of the
WPN were established by dynamic mechanical analysis (DMA)
via the tensile mode. The oscillation stress sweep test reveals a
linear response of the storage modulus (E′) and loss modulus
(E″) until the specimen broke at the critical oscillation stress of
0.8 MPa (Figure 4a). The frequency sweep test also shows that
both E′ and E″ remain relatively constant over a wide range of
frequencies (10−2−102 rad s−1) (Figure 4b). The thermomechan-
ical stability of the WPN was further evaluated by the tempera-
ture-dependent DMA test (Figure 4c). The thermomechanical
spectra exhibit a room temperature E′ value of ~385 MPa, and
the high-modulus regime extends from −20 to 120 °C. Further-
more, the tensile test was performed on the WPN. As the stress-
strain curve shown in Figure 4d, the WPN afforded the maxi-
mum tensile strength and strain values of 10.4 MPa and 2.9%,
respectively. These results suggest that the WPN possesses
good mechanical strength (Young’s modulus = 358 MPa), ther-
momechanical stability, and a certain level of ductility. There-
fore, we reasoned that weaving on the molecular level is able to
endow the resultant woven materials with improved mechanical
robustness, as observed in the case of macroscopic fabrics.
The mechanical properties of the WPN before and after
demetalation were studied using atomic force microscopy
(AFM) nanomechanical mapping.50,51 The AFM modulus dis-
tribution profiles of the WPNs are asymmetrical (Figure 5a and
b) and diverge from the Gaussian distribution (Figure S29a and
b). We speculate that the asymmetrical distribution stems from
the mismatch of the moduli between rigid and flexible parts in
the WPNs. Thus, each distribution profile of these two samples
was deconvoluted into two Gaussian curves and the reliability
of the fitting results was revealed by the high correlation coef-
ficient (R2 = 0.9914 for the WPN and R2 = 0.9957 for the
demetalated WPN).51 The two fitted curves in each profile could
be assigned to the flexible alkyl chains and rigid crossing points,
respectively. Notably, the demetalated WPN has a narrower
modulus distribution profile (Figure 5b), which indicates a
more uniform modulus distribution achieved upon removal of
zinc from the network. Compared with the original WPN, the
modulus assigned for the flexible chains in the demetalated
sample has a slight increase of 0.4 MPa, while the one contrib-
uted by the rigid parts undergoes a moderate decrease of 2.3
MPa (Figure 5a and b). These observations imply that the
threads in the demetalated WPN have more degrees of freedom
for spatial movements to average the modulus distribution in-
side the network. Meanwhile, the adhesion force mapping ex-
periments reveal that the distribution of adhesion forces became
more uniform after removing the metal centers (Figure 5c and
d), which can be attributed to the relatively loose structure of
the demetalated WPN.
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Besides, we also employed DMA to evaluate the thermome-
chanical properties of the demetalated and remetalated WPNs
(Figures S26 and S27). By comparison, we found that the me-
chanical and dynamic behaviors of these WPNs could be read-
ily tuned. For example, the Young’s modulus of the WPN de-
creased from 358 to 15.2 MPa upon demetalation, while the
value recovered up to 249 MPa by remetalation (Figure S28a).
Notably, the mechanical performance of the WPN cannot be
fully restored upon remetalation because the Schiff-base double
bonds were reduced to facilitate the removal of the Zn ions. The
reduction not only weakens the rigidity of the WPN, but also
changes the binding strength of the coordination bonds of the
crossing points, further boosting the mechanical adaptivities of
the WPNs.
Figure 5. AFM modulus distribution profiles and Gaussian fitting
results of the WPN (a) and demetalated WPN (b). Adhesion images
of the WPN (c) and demetalated WPN (d).
Conclusion
In summary, we presented a topological transformation strat-
egy for the design and construction of woven polymer networks
(WPNs) via ROMP of a [2]catenane. The structural transfor-
mation from discrete [2]catenane to infinite WPN was demon-
strated by the combination of various spectroscopic experi-
ments and theoretical simulation. The synergistic combination
of rigid crossing points and flexible alkyl chains in the WPN
endows the molecular fabric with flexible and ductile features,
as well as emergent mechanical performance including high
The octahedrally coordinated Zn(II) center plays a critical
role in maintaining the crossing points in the WPN during the
topological transformation via ROMP. Therefore, we are inter-
ested in removing the metal to prepare pure organic WPN and
inspect the properties of the WPNs before and after demeta-
lation. Reduction of the imine groups followed by washing with
aqueous EDTA produced the demetalated WPN.35 It was found
that ~98% of the Zn(II) ions had been removed based on the
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Sangji, H.; Luijten, E.; Stupp, S. I. Reversible Self-assembly of Super-
structured Networks. Science 2018, 362, 808−813.
6. Liu, Y.; Ma, Y.; Zhao, Y.; Sun, X.; Gándara, F.; Furukawa,
modulus and thermomechanical stability. In addition, by the re-
versible removal and addition of Zn(II) ions in the crossing
points, the WPN exhibits favorable tunability over its mechan-
ical and dynamic behaviors, while also retaining its structural
stability. This unique feature, in addition to its simplicity and
efficiency, make the molecular weaving strategy developed
here a great approach to mechanically adaptive materials. In
terms of the vast range of noncovalent interactions that are able
to hold building blocks in crossover geometries, we anticipate
the development of a variety of novel woven polymeric materi-
als for specific applications that are hardly achieved by tradi-
tional (supra)polymeric materials with covalent or non-woven
dynamic crosslinks.
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ASSOCIATED CONTENT
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Supporting Information Available. Experimental details and ad-
ditional data. This material is available free of charge via the Inter-
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(MIMs)—Molecular Shuttles, Switches, and Machines (Nobel Lec-
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AUTHOR INFORMATION
Corresponding Author
*xzyan@sjtu.edu.cn (X.Y.)
Author Contributions
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The manuscript was written through contributions of all authors.
All authors have given approval to the final version of the manu-
script. ⊥G.L., L.W., and L.W. contributed equally to this work.
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The authors declare no competing financial interest.
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X.Y. acknowledges the financial support of the NSFC/China
(21901161) and start-up funds from Shanghai Jiao Tong University.
L.W. acknowledges young researcher start-up fund from Shanghai
Jiao Tong University.
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