Journal of
Materials Chemistry A
COMMUNICATION
A photo-driven metallo-supramolecular stress-free
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Cite this: J. Mater. Chem. A, 2021, 9,
reversible shape memory polymer†
6827
Guancong Chen,a Binjie Jin,a Qian Zhao
Received 5th February 2021
Accepted 3rd March 2021
DOI: 10.1039/d1ta01111a
rsc.li/materials-a
Soft machines can offer remote-powering mechanisms and
mechanical flexibility unmatched by conventional rigid machines.
However, the molecular integration of powering and actuation func-
tions in a simple yet versatile format has remained challenging. We
achieve this with a semi-crystalline supramolecular metallo-network.
The dynamic metallo-bonds offer a flexible mechanism for
programming the network anisotropy, which gives rise to stress-free
reversible actuation using the crystalline transition as the actuation
phase. In addition, the proper choice of metallo-bonds provides
suitable photo-thermal capabilities for remote powering without
endangering the cyclic actuation stability, despite the supramolecular
nature. Based on these principles, we illustrate that the supramolec-
ular network can be programmed into a reptile-style device remotely
powered by light. The molecularly integrated dual functionality based
on supramolecular metallo-bonds provides an attractive option for
the future design of soft machines with sophisticated morphing
behaviors yet simple powering mechanisms.
Introduction
The emergence of so machines1–4 has led to many unusual
opportunities not offered by conventional rigid machines,
including human–machine interfaces,5 exible electronics,6
and minimally invasive medical devices.7 The operation of so
machines requires a combination of power and transmission,
much like rigid machines (e.g., cars). A particularly relevant
example is dielectric elastomers,8 which use an external elec-
trical supply to power the dielectric elastomer, i.e., the actuator
or “transmission”. A more widely accessible form of power for
driving the actuation of a so machine is direct heating and
cooling.9–11 This type of thermal powering presents a general
a
State Key Laboratory of Chemical Engineering, College of Chemical and Biological
Engineering, Zhejiang University, Hangzhou 310027, China
b
ZJU-Hangzhou Global Scientic and Technological Innovation Center, Hangzhou
311215, China. E-mail: taoxie@zju.edu.cn
† Electronic supplementary information (ESI) available. See DOI:
10.1039/d1ta01111a
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ab
and Tao Xie *ab
platform for developing the molecular design of thermally
responsive so actuators without having to integrate a dedi-
cated power unit. The downside is that it does not offer high
precision or freedom when it comes to machine control. Other
actuators driven by moisture12 or organic vapor13 operate simi-
larly, via capturing energy from a specic environment, but they
also suffer from the same issue.
The use of light offers a highly attractive powering mecha-
nism for so machines.14–20 Its remote nature and the potential
for spatiotemporal control provide versatility unmatched by
other mechanisms. Light-responsive so machines can operate
via two different mechanisms. The rst is achieved via inte-
grating intrinsic light-responsive molecular units into actua-
tors. Classical examples here are azobenzene-based liquid
crystalline elastomers (LCEs), in which the light-driven cis–trans
transition of azobenzene units converts the light energy into
mechanical motion.14–17 While elegant, this mechanism cannot
be broadly applied to most actuators. The second mechanism
utilizes photo-thermal effects.18–23 In principle, it can be readily
applied to any thermo-responsive actuators via incorporating
photo-thermal llers. This can be accomplished via coating
with a photo-thermal layer18 or incorporating photo-thermal
llers into the actuator matrix.19–23 In the former case, having
a robust coating that can sustain repeated actuation cycles is the
main concern. The latter case involves the challenge of
obtaining well-dispersed ller while not interrupting the
molecular order that is essential for actuation.21
From the standpoint of the actuator, the use of LCEs is
a popular choice due to its large strain capabilities.9,14–16,20–23
Recently emerged reversible (or two-way) shape memory poly-
mers (rSMPs)24–34 have also gained increasing traction. Unlike
LCEs, which rely on a liquid crystalline transition for actuation,
rSMPs operate via a synthetically more accessible crystalline
transition. They are capable of reversible actuation similar to
LCEs, yet they can be designed with more freedom due to the
larger pool of crystalline polymers. Enabling reversible actua-
tion in SMPs requires building an anisotropic crystallizable
polymer network.29,33 This is typically accomplished via
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Journal of Materials Chemistry A
imposing a stress-xing phase or covalent post-crosslinking on
a mechanically stretched network.24–34 In this work, we explore
the design of a light-driven so machine via the construction of
a metallo-network of a semi-crystalline polymer. The supra-
molecular nature of the metal ligand bonds35–37 provides
a different mechanism to lock-in the network anisotropy
required for a rSMP. In addition, the metal ligand moieties
naturally introduce photo-thermal capabilities for light power-
ing35 without having to resort to photothermal llers. Our
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photo-driven stress-free rSMP is notably different from a stress-
induced rSMP utilizing Fe3O4 as the photothermal ller.38
Herein, “stress-free” means it does not require the existence of
external stress during reversible actuation and, thus, the actu-
ator can operate in free-standing form. We illustrate the benet
of this difference via constructing a photo-driven reptile-style
device; this is otherwise difficult with a rSMP that requires
external stress during actuation.38 Our “one stone, two birds”
approach simplies the molecular design while offering greater
versatility for remotely powered so machines.
Results and discussion
A rst set of covalent networks was synthesized via reacting
terpyridine–polycaprolactone–acrylate (TPyA, Mn ¼ 5000) and
polycaprolactone diacrylate (PCLDA, Mn ¼ 10 000) with tetrakis
(3-mercaptopropionic acid)pentaerythritol ester (PTME) in the
presence of triethyl amine as the catalyst (Fig. 1a). Under these
conditions, the reaction between the acrylates and thiol pro-
ceeded in a click manner and they remained in stoichiometric
balance in all formulations. Accordingly, a series of networks
was synthesized via varying the ratio between TPyA and PCLDA.
The products are denoted as TPyX, with X representing the
weight percentage of TPyA monomer with reference to the total
acrylate amount. Representative infrared spectra before and
aer the crosslinking reaction (Fig. S1†) suggest a complete
reaction judging from the disappearance of the peak charac-
teristic to acrylate double bonds.
Fig. 1 The synthesis and actuation programming of the crystalline
metallo-network: (a) the precursors and synthesis of the network; and
(b) actuation programming.
6828 | J. Mater. Chem. A, 2021, 9, 6827–6830
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Fig. 1b illustrates the process of programming the networks
to allow reversible actuation. First, a network sample was
heated to a melt state. Pre-stretching deformation was imposed,
and the sample was immersed in a DMF solution of Fe2+ to
establish supramolecular metallo-bonds between the terpyr-
idine (TPy) moieties and Fe2+ ions. Upon releasing the stretch-
ing force, some of the network anisotropy due to stretching was
locked into the network via the metallo-bonds. This gave rise to
rSMP-based reversible actuation behavior. Notably, the molec-
ular design here forgoes the need for either the two crystalline
phases that are required in most rSMP systems24,25 or the post-
covalent crosslinking capabilities needed by other rSMPs.11–29
Various factors that impact the networks before metal-ion
chelation are presented in Fig. 2a–c. First, all the networks
show very similar melting temperatures (54  C) and crystallin-
ities (Fig. 2a), with the latter based on the enthalpy values cor-
responding to the melting peak areas. We note that samples
with higher TPyA fractions show insignicant double melting
peaks; this is likely due to the difference in the molecular
weights of PCL in TPyA and that in PCLDA. The swelling kinetics
in DMF are displayed in Fig. 2b. All the samples reach equi-
librium swelling at an identical time of around 40 min, which
establishes the basis for metal-ion chelation at a later stage. The
network gel fraction decreases with an increase in the TPy
weight fraction, whereas the equilibrium swelling ratio follows
an opposite trend (Fig. 2c). These two observations are consis-
tent with the mono-functional nature of TPyA, which does not
contribute to crosslinking. Importantly, the gel fractions are all
above 94%, suggesting good network formation in all cases.
Fig. 2d presents the metal-ion chelation behaviors of the
network samples. Chelation was conducted via immersing the
samples in DMF solutions of Fe2+ ions. A small amount of HCl
(0.02%) was added to the solutions, which can effectively
prevent the oxidation of Fe2+ (Fig. S2a†). The concentration of
Fe2+ ions in DMF solution was adjusted individually for each
sample based on a 2 : 1 molar ratio between TPy and Fe2+ ions.
This was necessary to ensure that one Fe2+ ion underwent
Fig. 2 Characterization of the metallo-networks: (a) DSC curves of the
networks; (b) swelling kinetics curves; (c) gel fraction and equilibrium
swelling ratios; and (d) the Fe2+ weight fractions in the networks.
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Communication
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Fig. 3 The reversible actuation of the metallo-networks: (a) the
impact of the TPy fraction on the reversible actuation strain; (b) the
impact of the pre-stretching strain on the reversible actuation strain
for TPy30; (c) consecutive reversible shape memory cycles for TPy30
(pre-stretching strain: 600%); and (d) a demonstration of the reversible
actuation for TPy30 (pre-stretching strain: 600%).
coordination with two TPy units instead of undergoing mono-
coordination. Upon using this protocol, we found that the
Fe2+ weight fractions for the samples aer chelation are
consistent with the calculated theoretical values (Fig. 2d). The
small discrepancies between the experimentally determined
Fe2+ fractions and theoretical values most likely arise from
small amounts of non-coordinated ions on the sample surfaces.
Having established the chelation procedure, we proceeded to
evaluate the programmed reversible actuation performance of
the supramolecular networks. Fig. 3a shows that, following
identical pre-stretch strains of 400% being applied during
programming (Fig. 1b), the resulting actuation strain increases
initially with the TPy fraction when it is less than 30%. This is
because TPy plays the critical role of providing the stress-locking
required for reversible actuation. A further increase in the TPy
fraction beyond 30% leads to a decrease in actuation, since the
fraction of PCL in the network mainframe (from PCLDA), which
contributes to actuation, is reduced. We chose TPy30 for further
investigation hereaer given its highest actuation strain. Its DSC
curve is presented in Fig. S2b,† showing a crystallization
temperature of 33  C and a melting temperature of 54  C. For this
sample, the actuation strain was found to increase linearly with
the pre-stretching strain, but that rate of increase was tapered
when the pre-strain was above 500%. Nevertheless, a maximum
reversible strain of 37% was achieved at a pre-strain level of
600%. This strain value is much higher than other crystalline
rSMPs (typically around 20%).24–34 Importantly, cycling tests show
highly consistent actuation behavior, with hardly any noticeable
deterioration between cycles (Fig. 3c). This suggests that the
metallo-bonds are robust in this temperature range (0–65  C),
despite their supramolecular nature. The high strain actuation is
visually illustrated in Fig. 3d, which shows a large length change
for a rectangular sample.
The TPy–Fe2+ coordination moieties endow the metallo-
network with photo-thermal capabilities. Fig. 4a compares the
light-induced time evolutions of temperature (upon exposure to
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Fig. 4 The light-driven actuation of TPy30: (a) the photo-thermal
heating kinetics; (b) a comparison of the photo-thermal effects
between TPy30 and TPy0; (c) light-driven reversible bending actua-
tion; and (d) the light-driven crawling of the soft machine (all scale
bars: 5 mm).
xenon light; 290 mW cm2) of TPy30 and TPy0. The temperature
increase was much more rapid for TPy30 and it reached a higher
ultimate temperature of 72  C. Aer approximately 110 s, the
temperature of TPy30 was 65  C, sufficiently higher than the
melting temperature for actuation. In contrast, even the highest
temperature of TPy0 aer 360 s was well below the melting
temperature. Here, the relatively minor temperature increase
for TPy0 was due to the convention of heat from the light
source. The large difference in remote heating upon light
exposure between the two samples is directly demonstrated in
Fig. 4b, showing a difference around 26  C aer the same
exposure time of 240 s. To move beyond linear length changes,
we fabricated a sample with a curled shape and subjected it to
the same programming procedure (Fig. S3†). Although the
sample experienced some minor distortion due to swelling
during programming, it displayed large reversible bending
actuation (Fig. 4c) upon heating and cooling. By turning the
light on and off, the reversible bending allows the sample to
crawl forward continuously on a designed track (Fig. 4d). A
video capturing the live action of this so machine is provided
in Movie S1.†
Conclusions
In summary, we present above a supramolecular approach for
designing so machines powered remotely by light using
a rSMP, with metallo-bonds providing molecularly integrated
dual functionality (remote powering and actuation). Although
we focused on Fe2+ in this work, it is foreseeable that many
other metal ions can potentially be employed for the same
purpose, which would offer the freedom to further tailor the
actuation and photo-thermal performances. Due to the supra-
molecular nature of the programming, the so machine can
potentially be reset via removing the ions and doping with
different ions. Another interesting possibility is to control the
spatial distribution of ions,36,37 which could give rise to more
complex movement. Combining the above strategies would
allow access to so machines with diverse motion using the
same polymer, which is our future direction of research. In
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Journal of Materials Chemistry A
addition, the underlying principle is not limited to rSMPs but
can be expanded to a variety of other actuators, including LCEs.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
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This work was supported by the following programs: the
National Natural Science Foundation of China (No. 52033009
and 21625402). The authors also thank Mrs Li Xu at State Key
Laboratory of Chemical Engineering (Zhejiang University) for
her assistance in performing DSC analyses.
Notes and references
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