A Mortise-and-Tenon Joint Inspired Mechanically Interlocked Network

Article abstract of DOI:10.1002/anie.202105620

Mortise-and-tenon joints have been widely used for thousands of years in wooden architectures in virtue of their artistic and functional performance. However, imitation of similar structural and mechanical design philosophy to construct mechanically adaptive materials at the molecular level is a challenge. Herein, we report a mortise-and-tenon joint inspired mechanically interlocked network (MIN), in which the [2]rotaxane crosslink not only mimics the joint in structure, but also reproduces its function in modifying mechanical properties of the MIN. Benefiting from the hierarchical energy dissipative ability along with the controllable intramolecular movement of the mechanically interlocked crosslink, the resultant MIN simultaneously exhibits notable mechanical adaptivity and structural stability in a single system, as manifested by decent stiffness, strength, toughness, and deformation recovery capacity.

Full text of DOI:10.1002/anie.202105620

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
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Accepted Article
Title: A Mortise-and-Tenon Joint Inspired Mechanically Interlocked
Network
Authors: Dong Zhao, Zhaoming Zhang, Jun Zhao, Kai Liu, Yuhang
Liu, Guangfeng Li, Xinhai Zhang, Ruixue Bai, Xue Yang, and
Xuzhou Yan
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202105620
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10.1002/anie.202105620
Angewandte Chemie International Edition
RESEARCH ARTICLE
A Mortise-and-Tenon Joint Inspired Mechanically Interlocked
Network
Dong Zhao,a Zhaoming Zhang,a Jun Zhao,a Kai Liu,a Yuhang Liu,a Guangfeng Li,a Xinhai Zhang,a
Ruixue Bai,a Xue Yang,a and Xuzhou Yan*a
[a]
Dr. D. Zhao, Dr. Z. Zhang, J. Zhao, Dr. K. Liu, Y. Liu, Dr. G. Li, Dr. X. Zhang, R. Bai, X. Yang and Prof. X. Yan
School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules
Shanghai Jiao Tong University, Shanghai 200240, P. R. China
E-mail: xzyan@sjtu.edu.cn
Supporting information for this article is given via a link at the end of the document.
Abstract: Mortise-and-tenon joints have been widely used for
thousands of years in wooden architectures in virtue of their artistic
and functional performance. However, imitation of similar structural
and mechanical design philosophy to construct mechanically adaptive
materials at the molecular level represents a challenging goal. Herein,
we report a mortise-and-tenon joint inspired mechanically interlocked
network (MIN), in which the [2]rotaxane crosslink not only mimics the
joint in structure, but also reproduces its function in modifying
mechanical properties of the MIN. Benefiting from the hierarchical
energy dissipative ability along with the controllable intramolecular
movement of the mechanically interlocked crosslink, the resultant MIN
simultaneously exhibits notable mechanical adaptivity and structural
wooden buildings oftentimes showcase great seismic
performance. Inspired by the elegant structure, we envision that
polymer networks with crosslinks resembling the mortise-and-
tenon joint may simultaneously combine the mechanical
robustness and stability of CPNs as well as dynamic and
responsive features of SPNs. However, the joint-like crosslinks
are quite rare on account of their complicated and delicate
topological structures along with the inherent adaptive properties.
[2]Rotaxanes, one of the most basic constituents of
mechanically interlocked molecules (MIMs), involve one wheel on
a dumbbell shaped axle.[7] The fascinating topological structure
allows for controllable intramolecular movement of the interlocked
stability in a single system, as manifested by decent stiffness, strength, components but still keeps structural integrity. As such, they have
toughness, and deformation recovery capacity. The present research
provides a structurally mimetic strategy toward mechanically robust
yet dynamic mechanically interlocked polymers, which will facilitate
the progress and application of mechanically interlocked molecules in
intelligent materials.
found promising applications in a variety of areas such as
interfacial cargo delivery, precise synthesis of biomolecules, and
artificial molecular machines.[8] Particularly, the [2]rotaxane is
structurally similar to the mortise-and-tenon joint, in which the
wheel resembles the mortise, the axle resembles the tenon, and
the recognition site on the axle resembles the wedge that is able
to stabilize the delicate structure. Along this line, [2]rotaxanes
would be a great candidate for the design of our expected polymer
networks.
Introduction
Herein, we report
a
mortise-and-tenon joint inspired
Over the last century, crosslinked polymer networks have
played essential and ubiquitous roles in a wide range of fields
owing to their attractive mechanical properties.[1] Depending on
the nature of the crosslinks, the polymer networks could be
classified into covalent polymer networks (CPNs) and
supramolecular polymer networks (SPNs), wherein the former
features permanent crosslinks (Figure 1a) and the latter
possesses dynamic crosslinks (Figure 1b).[2] Generally, CPNs
exhibit mechanical robustness but lack of dynamic property.[3] In
contrast, while dynamic crosslinks could endow SPNs with
reversible stimuli-responsiveness, they have also affected the
stability and strength of the networks.[4] As such, the development
of novel polymer networks with integrated dynamic stability and
mechanical adaptivity has been a long-standing pursuit of
chemists and materials scientists, although it still remains a
significant challenge.
mechanically interlocked network (MIN) which well integrates
dynamic stability and mechanical adaptivity in a single system,
and thus exhibits attractive mechanical properties (Figure 1c).
Specifically, the dibenzo-24-crown-8 (DB24C8) wheel is able to
be pulled away from the thermodynamically favored recognition
site of the dibenzylammonium salt (DBAS) under tension, thereby
endowing the MIN with dynamic behavior and energy dissipation
ability. At the same time, the mechanical bond not only links the
constituents together in a similar manner that covalent bond does,
but also shows mechanical strength comparable to the covalent
counterpart,[9] which would thus guarantee mechanically robust
and stable properties of the MIN.
Results and Discussion
In ancient wooden buildings, the mortise-and-tenon joint has
been widely used due to its combination of remarkable strength
and durability, simplicity, as well as the elegance of its
appearance.[5] In addition, because the mortise and tenon are
joined physically, the joint brings both dynamic and robust
features to the architecture and the features could be further
modulated by a wedge (Figure 1c).[6] By virtue of these merits,
To demonstrate our design, we chose DB24C8 and DBAS as
the complementary host−guest pair to construct tetraolefin
[2]rotaxane 1 (Scheme S1).[10] Photo-induced, radical-mediated
thiol-ene click chemistry was employed to prepare the
mechanically interlocked network (MIN-1) (Figure 1c). As a
comparison, we also constructed a “wedge-free” [2]rotaxane 2 via
1
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10.1002/anie.202105620
Angewandte Chemie International Edition
RESEARCH ARTICLE
Figure 1. Schematic representation of the three types of polymer networks. a) Covalent polymer network with permanent crosslinks. b) Supramolecular polymer
network with dynamic crosslinks. c) The mortise-and-tenon joint inspired design and preparation of polymer network with mechanically interlocked crosslinks.
N-acetylation of the sec-ammonium salt moiety of the [2]rotaxane
1[11] followed by the same thiol-ene click reaction to generate MIN-
2 (Scheme S1).
values were measured to be 30 and 24 °C for MIN-1 and MIN-2,
respectively (Figure 3a). We inferred that the distinction between
the Tg values could be attributed to the suppressed degree of
freedom of the polymer framework enabled by the host−guest
recognition, which behaved like a wedge stabilizing the mortise-
and-tenon joint. Moreover, dynamic mechanical analysis (DMA)
was carried out to discriminate the thermomechanical behaviors
of MINs. As shown in Figure 3b, the storage modulus (E′) of MIN-
1 was higher than that of the MIN-2, which was also ascribed to
the contribution of the host−guest recognition. Moreover, after
We firstly employed 1H NMR measurement to prove the
preparation of the [2]rotaxane monomers (Figures S21 and S24).
Partial 1H NMR spectra of DB24C8 wheel, [2]rotaxane 1, and
DBAS axle are shown in Figure 2. Upon the formation of
[2]rotaxane 1, the aromatic protons of H2, H3, and ethyleneoxy
protons H5−7 on the DB24C8 wheel as well as protons Hc and Hd
of the DBAS axle shifted upfield. Meanwhile, the methylene
protons He experienced downfield shift. These observations
originated from the combination of the macrocyclic shielding
effect and [N−H⋅⋅⋅O] and [C−H⋅⋅⋅O] hydrogen bonds. In addition,
the appearance of protons Ha on the triazole units and Hb on the
m-xylene stoppers confirmed the success of the stoppering
reaction. After treating [2]rotaxane 1 with acetic anhydride and
trimethylamine, the neutral and asymmetric [2]rotaxane 2 was
generated, which was proved by the complicated and split NMR
proton signals (Figure S27). These two [2]rotaxanes were also
ascertained by 13C NMR spectra (Figures S22 and S25) and
electrospray ionization mass spectrometry (ESI-MS) (Figures S23
and S26). Then, we employed the two [2]rotaxanes as
mechanically interlocked crosslinks to construct the MINs via
facile
thiol-ene
chemistry,
and
the
completion
of
photopolymerization was confirmed by fourier transform infrared
spectroscopy (FT-IR) (Figure S28). The swelling experiments of
the MINs further indicated the formation of crosslinked networks
(Figure S29).
After the preparation of MINs, we investigated their thermal
properties. Thermal gravimetric analysis (TGA) exhibited that the
decomposition temperatures of both MIN-1 and MIN-2 were
higher than 250 °C, indicating good thermal stability (Figure S30).
The differential scanning calorimetry (DSC) of the two samples
were also conducted and the glass transition temperature (Tg)
Figure 2. Partial 1H NMR spectra (400 MHz, CDCl3, 298 K) of a) DB24C8 wheel,
b) [2]rotaxane 1, and c) DBAS axle.
2
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10.1002/anie.202105620
Angewandte Chemie International Edition
RESEARCH ARTICLE
undergoing glass transition, the MINs still exhibited pronounced
plateaus and their E′ values were much larger than those of loss
moduli (E″), suggestive of good elastic behaviors and
thermomechanical stability of the networks.
the DB24C8 wheel could be responsible for the energy dissipation
of the MIN-2, which would also occur in MIN-1 when the wheel is
pulled away from the DBAS site.[12] In addition, the hysteresis
areas of the loading-unloading cycle of MIN-1 were larger than
those of the MIN-2 with the same strains, reflecting the role of
host−guest dissociation in energy dissipation (Figure 4c).
Therefore, these results suggested that both the host−guest
binding and intramolecular motion of the wheel on the axle
contributed synergistically to the energy dissipation of MIN-1.
Then, we wondered what would happen after the DB24C8
wheel was slid away from the recognition site. To study this issue,
we conducted cyclic tensile tests in which the MIN-1 was
repeatedly loaded to a 40% strain and unloaded with different rest
intervals ranging from 0 to 40 min (Figure 4d). The second circle
Furthermore, we studied the wedge effect of the crosslinks on
the mechanical properties of the MINs via tensile tests. As shown
in Figure 3c and d, MIN-1 was found to exhibit favorable
mechanical performance including higher stiffness (Young’s
modulus = 246 MPa), strength (maximum stress = 15.5 MPa), and
toughness (12.9 MJ/m3) than those of the MIN-2 (Young’s
modulus = 145 MPa, maximum stress = 9.95 MPa, and toughness
= 7.40 MJ/m3). Just like the fixing function of the wedge in the
mortise-and-tenon joint, the host−guest recognition in crosslinks
made an improvement in the mechanical features of the MINs.
Moreover, there is no obvious difference in terms of fracture strain
of the MIN-1 (106%) and MIN-2 (108%) (Figure 3c). The
comparable results could be explained that these two MINs have
very similar network structures.
without relaxing showed
a much smaller hysteresis loop
compared with the first one. Moreover, a large residual strain was
also observed. The phenomena were related to the dissociation
and movement of the DB24C8 wheel along the axle, but which
could basically restore when the relaxing time was extended to 20
min. Compared with MIN-2, the recovery of MIN-1 was slightly
faster because of the existence of host−guest interaction (Figures
S34 and S35). Notably, although it was not as good as MIN-1, the
deformation recovery of MIN-2 was comparable to most of the
reported elastomers,[13] which was probably due to the role of the
stopper in restricting further movement of the DB24C8 wheel.
Figure 3. a) DSC curves of MIN-1 and MIN-2 recorded by the second heating
scan from −40 to 100 °C with a heating rate of 20 °C/min. b) DMA curves of the
MINs recorded during the heating process from −35 to 100 °C with a heating
rate of 5.0 °C/min. c) Stress-strain curves of MIN-1 and MIN-2 recorded with a
stretching rate of 100 mm/min. d) Young’s moduli and toughness of MIN-1 and
MIN-2 calculated based on their stress-strain curves.
The above results have revealed that the host−guest interaction
could stabilize the mechanically interlocked crosslinks and thus
make them more robust. In essence, the host−guest recognition
is also dynamic and reversible because of its noncovalent nature.
To clarify this issue, a series of measurements were performed.
The results of stress relaxations were shown in Figure 4a. Under
different strains (3%, 5%, and 10%), similar stress-relaxation
behaviors were observed: the stress dropped rapidly in the initial
part of the test followed by a gradual relaxation at a longer time.
In addition, the stress relaxation decreased as the strain
increased, namely, higher strain led to lower relaxation. The
considerable stress-relaxation of MIN-1 might be related to the
contribution of the dynamic mechanically interlocked crosslinks.
The dynamic character of the crosslinks was further revealed
by cyclic tensile tests (Figure 4b). For different applied strains
(from 10 to 60%), large hystereses were observed for MIN-1 after
reloading, which implied remarkable ability in energy dissipation.
It is worth noting that MIN-2 also exhibited pronounced hystereses
under the same conditions (Figure S33). Force-induced sliding of
Figure 4. a) Stress relaxation curves of MIN-1 at different pre-stretched strains.
b) Cyclic tensile test curves of MIN-1 with increased maximum strains. c)
Hysteresis areas of MIN-1 and MIN-2 calculated from each circle of cyclic tensile
test curves. d) Cyclic tensile test curves of MIN-1 loaded at a strain of 40% with
rest intervals ranging from 0 to 40 min. e) Schematic illustration of possible
sliding movement of the wheel on the axle under tension (left) and after the
release of external force (right). F is the external force and F′ denotes the driving
force of host−guest interaction.
Based on these results, we are able to deduce the working
mechanism of the mechanically interlocked crosslinks in the MINs.
On one hand, the dissociation of the host−guest recognition could
3
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10.1002/anie.202105620
Angewandte Chemie International Edition
RESEARCH ARTICLE
be regarded as an effective pathway to dissipate external force
(Figure 4e, left). And, once the DB24C8 wheel is pulled away from
the DBAS site, its motion on the axle could further dissipate
energy. Compared with CPNs, these dual dynamic properties
endow corresponding MIN with good mechanical adaptability and
unusual performance in energy dissipation. On the other hand,
the m-xylene stopper could prevent the deslipping of the DB24C8
wheel from the axle, which is beneficial to the stability and
deformation recovery capability of the MIN. Besides, host−guest
interaction as a driving force could also contribute to the
recombination of the dissociated wheel and axle. Hence, the MIN
would exhibit a faster rehabilitation of the deformed network
compared with general SPNs (Figure 4e, right). As such, the
stability of the MIN can be described as follows: the mechanically
interlocked crosslinks are stable under ambient conditions due to
the host−guest complexation, and even if it dissociates under
tension, the recovery of the crosslink is fast as a result of the
frequency displayed a marked relaxation process. The molecular
basis of the process lies in the motion of free ammonium groups,
which were released by the dissociation of DB24C8 and DBAS
under tension. By contrast, we couldn’t observe similar dielectric
relaxation behaviors on the samples of the unstretched MIN-1 as
well as MIN-2 with or without being stretched (Figure 5a).
In order to get more information about the host−guest
interaction in the mechanically interlocked joint, tensile tests with
different stretching rates were performed. As shown in Figure 5b,
the mechanical behaviors of the MIN-1 were highly dependent on
the deformation rate, indicative of the involvement of dynamic and
reversible host−guest interactions.[13b] Moreover, there was a
linear relationship between the yielding stress and the natural
logarithm of the strain rate, which was in accord with the Eyring
model of external force induced dissociation of noncovalent
bonds (Figures 5c).[14] The apparent activation energy used to
evaluate the energy barrier to overcome the mobile segments was
synergistic effect between the stopper and host−guest recognition. calculated to be 17 kJ/mol. In addition, the activation volume
Therefore, the mortise-and-tenon joint inspired mechanically
interlocked crosslinks impart both dynamic stability and
mechanical adaptability to the resultant MIN.
extracted by data fitting was 3.4 nm3, which reflected the size of
polymer segments involved in the motion associated with yielding.
In general, structural changes of networks should be responsible
for the yielding of elastomers. For MIN-1, the structural change is
more likely due to the sliding motion of DB24C8 wheel on the
DBAS axle. Therefore, we speculate that the energy to dissociate
the host−guest recognition and launch the motion of DB24C8
wheel is about 17 kJ/mol.
The versatile roles of the mechanically interlocked crosslinks in
MIN-1 could be further confirmed by the creep and recovery
experiments (Figure 5d). At the initial stage (< 300 s), the creep
rate of MIN-2 was much faster than that of MIN-1, and the curve
of MIN-2 tended to level off. During this process, the motion of
DB24C8 wheel in MIN-2 reached its equilibrium, but only basic
deformation of the network occurred in MIN-1, indicating the
wedge effect of host−guest recognition in stabilizing the network.
After that, acceleration of creep was observed for MIN-1, which
should be related to the gradual dissociation of host−guest
recognition and followed by the sliding motion of the DB24C8
wheel. When stress was removed, the recovery of strain for MIN-
1 was over 90% but that for MIN-2 was only 75%. As we
mentioned above, such a notable recovery performance of MIN-1
was beneficial from the synergistic effect of the stopper and
host−guest recognition. Therefore, the overall working process of
the mechanically interlocked crosslink was well exhibited by the
creep and recovery results, which further verified the proposed
mechanism.
Figure 5. a) Dielectric loss spectra of MIN-1 and MIN-2 measured at ‒30 °C. b)
Tensile behaviors of MIN-1 under different stretching rates. c) Fitting curve of
yielding stress as a function of logarithm of strain rate. d) Creep and recovery
behaviors of MIN-1 and MIN-2 at a constant stress of 0.5 MPa.
The hypothesized mechanism is based on the dissociation and
recombination of the DB24C8 and DBAS recognition in the MIN,
so it is necessary to understand such processes. To demonstrate
the dissociation of the DB24C8 wheel from the DBAS recognition
site under tension, dielectric relaxation spectroscopy (DRS)
measurements were carried out. Since the host−guest dynamics
of the MINs are quite sensitive to temperature, the dielectric
relaxation was deliberately separated into two regimes, namely,
above Tg and below Tg. At 50 °C (> Tg), we didn’t observe the
dielectric relaxation process for both MIN-1 and MIN-2 (Figure
S36), which can be explained that the dielectric permittivity and
loss were masked by strong direct current conductivity. We then
turned to run the test at −30 °C (< Tg). As shown in Figure 5a, the
dielectric loss spectrum of the stretched MIN-1 as a function of
Conclusion
In summary, inspired by the mortise-and-tenon joint, we
developed
a mechanically adaptive yet structurally stable
mechanically interlocked network (MIN) by means of facile thiol-
ene click chemistry of the tetraolefin [2]rotaxane and 3,6-dioxa-
1,8-octanedithiol. The sliding motion of the DB24C8 wheel on the
axle under tension endowed the MIN with dynamic behaviours
resembling SPNs. The unique interlocked structure of the
mechanical bond further led to the MIN with robust features, which
are comparable to CPNs. It is worth noting that energy dissipation
stemming from the dissociation of host−guest recognition and
consequential sliding motion of the DB24C8 wheel also
contributed to the mechanical behaviors of the MIN. In addition,
4
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10.1002/anie.202105620
Angewandte Chemie International Edition
RESEARCH ARTICLE
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mortise-and-tenon joint inspired molecular design would enable
encouraging applications of mechanically interlocked polymers as
advanced functional materials, such as mechanically adaptive
elastomers, anti-scratch coatings, and smart soft actuators.
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Acknowledgements
X.Y. acknowledges the financial support of the NSFC/China
(21901161 and 22071152), Natural Science Foundation of
Shanghai (20ZR1429200), and Shanghai Jiao Tong University
Scientific and Technological Innovation Funds.
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Keywords: mortise-and-tenon joint • host−guest chemistry •
mechanically interlocked molecules • mechanical adaptivity •
mechanically interlocked polymers
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10.1002/anie.202105620
Angewandte Chemie International Edition
RESEARCH ARTICLE
Entry for the Table of Contents
We demonstrated that the delicate mortise-and-tenon joint was precisely mimicked to construct a mechanically interlocked network
(MIN), which simultaneously integrates incompatible mechanical adaptivity, robustness, and dynamic stability in a single system.
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This article is protected by copyright. All rights reserved.