ChemComm
View Article Online
COMMUNICATION
A large room-temperature entropy change in a
new hybrid ferroelastic with an unconventional
Published on 17 July 2020. Downloaded by Universidad de la Coruna on 5/19/2022 9:40:56 AM.
Cite this: Chem. Commun., 2020,
56, 10054 bond-switching mechanism†
Received 11th June 2020,
Accepted 17th July 2020 Wei-Jian Xu, ab Ying Zeng,a Wei Yuan,a Wei-Xiong Zhang
Xiao-Ming Chen a
DOI: 10.1039/d0cc04092d
rsc.li/chemcomm
We showed a reversible bond-switching ferroelastic phase transi-
tion at near room temperature in a novel organic–inorganic hybrid,
(Me3NNH2)2[Co(CN)6Na(H2O)], to afford a latent heat of 43.7 kJ kg1
and a large entropy change of 146 J K1 kg1.
A large barocaloric effect (isothermal entropy change or adia-
batic temperature change upon application or withdrawal of
external hydrostatic pressure) is expected in the region where
ferroelasticity spontaneously emerges during a phase transi-
tion, which makes ferroelastics promising candidates for appli-
cations as solid-state cooling devices to replace present
refrigeration technologies.1–5 In the past decade, the explora-
tion of ferroelastics was extended to organic–inorganic hybrid
materials, profiting from their low weight, low acoustical
impedance, environmentally benign synthesis and structural
tunability. In particular, the past few years have witnessed
the emergence of numerous hybrid ferroelastics, such as
[Fe(Cp)2][FeCl4] with a narrow band gap of 1.61 eV,6 a chiral
hybrid ferroelastic with seven physical channel switches,7 a
spin-crossover hybrid ferroelastic displaying domain wall
motion,8 and (Me3NOH)2[ZnCl4] with a large spontaneous
strain of 0.129.9 However, the hybrid ferroelastic displaying a
large barocaloric effect is scarce. The main difficulty lies in the
understanding that the underlying phase transition mechan-
isms found in hybrid ferroelastics usually originate from con-
ventional order–disorder and/or displacive types, which are not
involved in breaking of the coordination bonds, and thus
generally contribute to small entropy changes. Nevertheless,
a
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of
Chemistry, Sun Yat-Sen University, Guangzhou 510275, China.
E-mail: zhangwx6@mail.sysu.edu.cn
b
Department of Chemistry & CICECO-Aveiro Institute of Materials, University of
Aveiro, 3810-193 Aveiro, Portugal
† Electronic supplementary information (ESI) available: Single-crystal structures,
thermogravimetric analysis, and powder X-ray diffraction patterns. CCDC
2003376 and 2003377. For ESI and crystallographic data in CIF or other electronic
format see DOI: 10.1039/d0cc04092d
10054 | Chem. Commun., 2020, 56, 10054--10057
View Journal | View Issue
*a and
ferroelastics that display very large barocaloric effects generally
require large reversible entropy changes and large levels of
dependence of the transition temperature on pressure, i.e.,
barocaloric coefficient (dTc/dP).10,11 In this sense, it is funda-
mentally important to search for new sources of ferroelastics to
promote the exploration of hybrid ferroelastic materials with
large entropy changes.
Bond-switching structural phase transition involving rever-
sible generation/cleavage of coordination bonds, with a certain
extent of order–disorder and displacement characteristics, is
not only of great academic interest but also of technological
importance. Such bond-switching transition with changes in
the coordination environments of metal ions would bring
drastic symmetry breaking that would facilitate a triggering of
the development ferroic-related properties and interconversion
of the spin state.12–17 Moreover, the entropy changes resulting
from a first-order bond-switching transition are substantially
larger than those resulting from conventional phase transitions.
For instance, we previously reported the first molecular double-
perovskite multiaxial ferroelectric, (Me3NOH)2[KFe(CN)6] (named
TMC-1), showing a bond-switching transition from a monoclinic
ferroelectric phase to a cubic paraelectric phase.12 Understanding
the mechanism of such an unconventional bond switching is thus
crucial for designing ferroic–caloric materials. Herein, we demon-
strated how to make use of the weaker and switchable coordina-
tion bonds to yield a reversible bond-switching ferroelastic
transition in a novel organic–inorganic hybrid, (Me3NNH2)2
[Co(CN)6Na(H2O)] (TMC-2), and afford a large entropy change
of 146 J K1 kg1 at room temperature. And a large volume
change during bond-switching transition gave rise to a large
barocaloric coefficient of 22.2 K kbar1, making TMC-2 of
particular interest for solid-state cooling applications at or near
room temperature. Such an unconventional bond-switching
transition being capable of affording a large entropy change
in a hybrid ferroelastic opens up a new strategy for the design of
hybrid ferroic–caloric materials for use in next-generation eco-
friendly solid-state refrigeration technologies.
This journal is © The Royal Society of Chemistry 2020
 View Article Online

Communication ChemComm
Published on 17 July 2020. Downloaded by Universidad de la Coruna on 5/19/2022 9:40:56 AM.

Fig. 1 (a and d) The asymmetric units of TMC-2 in the (a) FP and (d) PP; symmetry codes: (A) 1 + x, y, z; (B) 1  x, 1/2 + y, 1/2  z; (C) 1  x, 1/2 + y,
1/2  z; (D) 1 + x, y, z. (b and e) Simplified structural illustrations showing perspective views along the respective b-axes of the TMC-2 crystals in the (b) FP
and (e) PP; in each case the linkage of cyano groups is depicted by brown lines. (c and f) A comparison of selected structural units in the (c) FP and (f) PP.

TMC-2 was crystallized from an aqueous solution of Na3 To visualize the ferroelastic transition for TMC-2, variable-
[Co(CN)6] and (Me3NNH2)I in a ratio of 1 : 2 by carrying out a temperature polarization microscopy was performed on an
slow evaporation at room temperature. According to an in situ as-grown single crystal. After the first heating–cooling cycle,
variable-temperature X-ray diffraction analysis, TMC-2 crystal- stripe-like domain structures appeared in the (012) plane,
lized in the monoclinic space group P21/c at 200 K (ferroelastic confirming the occurrence of ferroelastic domains in the FP
phase, FP) (Table S1, ESI†). The asymmetric unit was found to (Fig. S6, ESI†). These stripes became clearer in the vicinity of
consist of two Me3NNH2+ cations, one [Co(CN)6]3 anion, one the phase transition point in a subsequent heating run. As
Na+, and one H2O (Fig. 1a). Here, each Na+ ion was located in a illustrated in Fig. 2b and d, well-defined diagonally aligned
distorted NaN5O octahedron and coordinated with five species: stripes were observed at 295 K, which well matched the predic-
two –NH2 groups from two Me3NNH2+ cations (Na–N10 = tions made by Aizu on the domain boundary orientation in the
3.023(1) Å, Na–N8 = 2.825(1) Å, Table S5, ESI†), three N atoms mmmF2/m species (see ESI† for the details of the deduction of
from the CN ligands (Na–N E 2.4 Å) and one H2O. Each domain orientation).23 Above the Tc, domain walls almost dis-
[Co(CN)6]3 anionic octahedron was observed to be connected appeared (Fig. 2c and e), while diagonal domain structures re-
to three neighboring Na+ ions via three bridging cyano groups, emerged upon further cooling to 280 K in the FP (Fig. 2f and g).
forming a two-dimensional (2D) bimetallic anionic layer in the Such reversible disappearance and appearance of domain walls
ab plane (Fig. 1b and Fig. S6a, ESI†). Both Me3NNH2+ cations provided evidence for the ferroelastic phase transition in TMC-2,
were found to interact with the anionic framework via weak
hydrogen bonds (N–H  N E 3.1 Å, Table S4, ESI†).
Upon heating above 300 K, the crystal structure transformed
into a paraelastic phase (PP) in the orthorhombic space group
Pmmn. Each Na+ became involved in a disordered tetrahedral
coordination geometry (NaN3O), thus resulting in a disordered
2D anionic layer as required by the imposed orthorhombic
symmetry in the PP (Fig. 1d). Interestingly, in the PP, all
Me3NNH2+ cations located in the space between the 2D layers
became coordination-free and showed two-fold disorder about
a mirror plane (Fig. 1e and f). Besides, the hydrogen bonds
between Me3NNH2+ cations and the 2D host layer became weaker
(N–H  N E 3.2 Å, Table S7, ESI†). In short, the observation of
switchable weak Na–N coordination bonds revealed for TMC-2 an
unconventional bond-switching phase transition quite different Fig. 2 (a–g) Evolution of the domain structure of TMC-2 in the heating–
from the common order–disorder and displacive transitions in cooling cycle. (h) The crystal morphology of TMC-2 (size: 0.6  0.4 
other hybrid ferroic-materials and plastic crystals.18–22 0.1 mm).

This journal is © The Royal Society of Chemistry 2020 Chem. Commun., 2020, 56, 10054--10057 | 10055
 View Article Online

ChemComm Communication

consistent with the symmetry reduction derived from the X-ray
diffraction structural analysis. The total spontaneous strain (ess)
was estimated to be 0.036, comparable to those of cadmium
thiocyanate hexagonal-perovskite ferroelastics (0.043–0.078),24 but
lower than those of (Me3NOH)2[ZnCl4] (0.129)9 and [Fe(Cp)2]
[FeCl4] (0.109).6 Such spontaneous strain can be mainly ascribed
to a lattice distortion during the bond-switching phase transition.
Temperature-dependent dielectric and differential scanning
calorimetry (DSC) measurements were taken to provide further
Published on 17 July 2020. Downloaded by Universidad de la Coruna on 5/19/2022 9:40:56 AM.
indirect Clausius–Clapeyron equation dTc/dP = DV/DS, where
DS is the aforementioned entropy change, and DV is the volume
change calculated from in situ single-crystal X-ray diffraction
(Table S8, ESI†). As shown in Fig. 3c, this entropy change of TMC-
2 was found to be greater than those, at ambient pressure, of
state-of-the-art barocaloric materials such as metal alloy Fe49Rh51
(12 J K1 kg1),31 ionic conductor AgI (64 J K1 kg1),32 spin
crossover compound [Fe(C11H9N5)](BF4)2 (86 J K1 kg1),33 and
ferroelectric compound (NH4)2SO4 (65 J K1 kg1),34 but smaller
than those of TMC-1 (178 J K1 kg1) and plastic crystal

insight into the bond-switching transition. The dielectric con-

stant measurements revealed a well-defined dielectric bistabil-
ity with a thermal hysteresis of ca. 18 K (Fig. 3a, top). This
observation was in good agreement with the DSC observation of
a pair of endothermic/exothermic peaks at 300/282 K during
the heating/cooling cycle, suggesting a first-order phase transi-
tion for TMC-2 (Fig. 3a, bottom).
Integration of the calorimetric peaks yielded latent heat
(|Q0|) values of 43.7 kJ kg1 and 41.2 kJ kg1 on the heating
and cooling runs, respectively. These values were much higher
than those of elastocaloric/barocaloric compounds (Fig. 3b), such
as inorganic BaTiO3 (0.13 kJ kg1),25 Mn3GaN (6.29 kJ kg1),3
hybrid perovskite (TPrA)Mn(dca)3 (14.0 kJ kg1),26 and
(DMA)[Mg(HCOO)3] (14.5 kJ kg1),27 but lower than that of
plastic crystal (CH3)2C(CH2OH)2 (110 kJ kg1).28–30
After several heating–cooling cycles of DSC measurements,
the average entropy change DS around the Tc was estimated to
be 146 J K1 kg1, indicating good reversibility of the entropy
change for TMC-2 (Fig. S8, ESI†). Furthermore, a barocaloric
coefficient (dTc/dP) of 22.2 K kbar1 was calculated by using the
(CH3)2C(CH2OH)2 (383 J K1 kg1).28–30 It is worth noting that
the entropy change of TMC-1 gradually decreased after several
cycles, and the plastic crystals having an intrinsic high deform-
ability generally did not rapidly and completely recover after
withdrawing the external pressure. Such irreversible characteris-
tics are unfavorable for many refrigeration cycles. In this sense, by
benefiting from good reversibility of a large entropy change, a
moderate phase transition temperature (i.e., near room tempera-
ture), and a large barocaloric coefficient, TMC-2 may be consid-
ered as an excellent barocaloric material candidate for solid-state
refrigeration applications in the room-temperature region.
X-ray diffraction structural analysis revealed a ratio of the
numbers of geometrically distinguishable cation orientations
in both FP and PP to be N = 2. Accordingly, if only taking into
account the contribution from order–disorder transition of
cations, a calculated DS of 14.3 J K1 kg1 could be expected
based on the Boltzmann equation DS = R ln(N), where R is the
gas constant. However, this calculated DS value is much lower
than the experimental one estimated from the DSC measurement.

Fig. 3 (a) Temperature dependence of the dielectric constant (e 0 ) of TMC-2 as measured using a pressed-powder pellet at 1 MHz in a heating–cooling
cycle (top) and DSC curves of TMC-2 (bottom). (b) Latent heats of TMC-2 and selected mechanocaloric materials. (c) Solid–solid phase transition entropy
change, transition temperature, and barocaloric coefficient data for state-of-the-art barocaloric materials and TMC-2. (d) A schematic illustration of a
refrigeration cycle of TMC-2 based on a bond-switching ferroelastic transition.

10056 | Chem. Commun., 2020, 56, 10054--10057 This journal is © The Royal Society of Chemistry 2020

Communication
Unsurprisingly, the cleavage and re-formation of weak Na–N
coordination bonds between organic cations and the anionic
inorganic layer mainly contributed to the entropy change, in
great contrast to the order–disorder transitions of molecular
configurations reported for the known barocaloric materials.
Therefore, we proposed a refrigeration mechanism based on
this new bond-switching ferroelastic transition (Fig. 3d). First,
applying sufficient pressure on TMC-2 at above 300 K (at the
PP) would cause a pressure-induced phase transition from the
Published on 17 July 2020. Downloaded by Universidad de la Coruna on 5/19/2022 9:40:56 AM.
PP to the FP, i.e., a transition of the organic cations from a
coordination-free state to a coordinatively bonded state, with a
release of a large amount of latent heat. Second, TMC-2 would
be made to return to its initial temperature by dissipating the
heat to the environment, and a heat sink is usually used to
facilitate such a process. Third, pressure on TMC-2 would be
released in order recover the coordination-free state of the organic
cations and to absorb a large amount of heat. Fourth, TMC-2
would be made to absorb heat from a heat source and return to its
initial temperature, thereby cooling the target heat source.
In summary, a new room-temperature hybrid ferroelastic,
i.e., TMC-2, was shown to exhibit a reversible first-order bond-
switching phase transition accompanied by a large entropy
change of 146 J K1 kg1. Furthermore, electrocaloric and
barocaloric effects were expected to be accomplished simulta-
neously in the hybrid ferroelectric with large entropy changes
for the development of multicaloric materials.35–37 This work is
expected to not only be helpful for deepening our understand-
ing of unconventional bond-switching phase transitions in
hybrid materials, but also for inspiring the pursuit of intriguing
further research into novel ferroic–caloric functional materials
based on the bond-switching mechanism.
This work was supported by the NSFC (21722107, 21671202,
21805312 and 21821003), and Local Innovative and Research
Teams Project of Guangdong Pearl River Talents Program
(2017BT01C161).
Conflicts of interest
There are no conflicts to declare.
Notes and references
1 X. Moya, S. Kar-Narayan and N. D. Mathur, Nat. Mater., 2014, 13, 439–450.
2 T. Ichiro and K. Sandeman, Phys. Today, 2015, 68, 48–53.
3 D. Matsunami, A. Fujita, K. Takenaka and M. Kano, Nat. Mater.,
2015, 14, 73–78.
4 L. Mañosa and A. Planes, Adv. Mater., 2017, 29, 1603607.
5 B. Lu and J. Liu, Sci. Bull., 2015, 60, 1638.
6 H.-Y. Zhang, C.-L. Hu, Z.-B. Hu, J.-G. Mao, Y. Song and R.-G. Xiong,
J. Am. Chem. Soc., 2020, 142, 3240–3245.
7 S.-Q. Lu, Z.-X. Zhang, H. Cheng, P.-F. Li, W.-Q. Liao and R.-G. Xiong,
Angew. Chem., Int. Ed., 2020, 59, 9574–9578.
8 G. G. Morgan, V. B. Jakobsen, E. Trzop, L. C. Gavin, E. Dobbelaar,
S. Chikara, X. Ding, K. Esien, H. Müller-Bunz, S. Felton, V. S. Zapf,
E. Collet and M. A. Carpenter, Angew. Chem., Int. Ed., 2020, DOI:
10.1002/anie.202003041.
This journal is © The Royal Society of Chemistry 2020
View Article Online
ChemComm
9 W. Yuan, Y. Zeng, Y.-Y. Tan, J.-H. Zhou, W.-J. Xu, W.-X. Zhang and
X.-M. Chen, Chem. Commun., 2019, 55, 8983–8986.
10 J. M. Bermúdez-Garcı́a, M. Sánchez-Andújar and M. A. Señarı́s-
Rodrı́guez, J. Phys. Chem. Lett., 2017, 8, 4419–4423.
11 L. Mañosa, A. Planes and M. Acet, J. Mater. Chem. A, 2013, 1,
4925–4936.
12 W.-J. Xu, P.-F. Li, Y.-Y. Tang, W.-X. Zhang, R.-G. Xiong and X.-M.
Chen, J. Am. Chem. Soc., 2017, 139, 6369–6375.
13 P. Szuromi, Science, 2017, 356, 817.
14 D. Aguilà, P. Dechambenoit, M. Rouzières, C. Mathonière and
R. Clérac, Chem. Commun., 2017, 53, 11588–11591.
15 V. I. Ovcharenko, S. V. Fokin, E. T. Kostina, G. V. Romanenko,
A. S. Bogomyakov and E. V. Tretyakov, Inorg. Chem., 2012, 51,
12188–12194.
16 M. C. Bernini, F. Gándara, M. Iglesias, N. Snejko, E. Gutiérrez-
Puebla, E. V. Brusau, G. E. Narda and M. Á. Monge, Chem. – Eur. J.,
2009, 15, 4896–4905.
17 P. Guionneau, F. Le Gac, A. Kaiba, J. S. Costa, D. Chasseau and J.-F.
Létard, Chem. Commun., 2007, 3723–3725.
18 Y. Tang, Z. Sun, C. Ji, L. Li, S. Zhang, T. Chen and J. Luo, Cryst.
Growth Des., 2015, 15, 457–464.
19 H.-Y. Ye, J.-Z. Ge, Y.-Y. Tang, P.-F. Li, Y. Zhang, Y.-M. You and R.-G.
Xiong, J. Am. Chem. Soc., 2016, 138, 13175–13178.
20 Y.-J. Cao, L. Zhou, P.-P. Shi, Q. Ye and D.-W. Fu, Chem. Commun.,
2019, 55, 8418–8421.
21 S.-S. Wang, X.-X. Chen, B. Huang, R.-K. Huang, W.-X. Zhang and X.-M.
Chen, CCS Chem., 2019, 1, 448–454.
22 H.-Y. Zhang, Y.-Y. Tang, P.-P. Shi and R.-G. Xiong, Acc. Chem. Res.,
2019, 52, 1928–1938.
23 K. Aizu, J. Phys. Soc. Jpn., 1969, 27, 387–396.
24 L. He, L. Zhou, P.-P. Shi, Q. Ye and D.-W. Fu, Chem. Mater., 2019, 31,
10236–10242.
25 E. Stern-Taulats, P. Lloveras, M. Barrio, E. Defay, M. Egilmez,
A. Planes, J. L. Tamarit, L. Mañosa, N. D. Mathur and X. Moya,
APL Mater., 2016, 4, 091102.
26 J. M. Bermúdez-Garcı́a, M. Sánchez-Andújar, S. Castro-Garcı́a,
J. López-Beceiro, R. Artiaga and M. A. Señarı́s-Rodrı́guez, Nat.
Commun., 2017, 8, 15715.
27 M. Szafrański, W.-J. Wei, Z.-M. Wang, W. Li and A. Katrusiak, APL
Mater., 2018, 6, 100701.
28 B. Li, Y. Kawakita, S. Ohira-Kawamura, T. Sugahara, H. Wang,
J. Wang, Y. Chen, S. I. Kawaguchi, S. Kawaguchi, K. Ohara, K. Li,
D. Yu, R. Mole, T. Hattori, T. Kikuchi, S.-I. Yano, Z. Zhang, Z. Zhang,
W. Ren, S. Lin, O. Sakata, K. Nakajima and Z. Zhang, Nature, 2019,
567, 506–510.
29 P. Lloveras, A. Aznar, M. Barrio, P. Negrier, C. Popescu, A. Planes,
L. Mañosa, E. Stern-Taulats, A. Avramenko, N. D. Mathur, X. Moya
and J. L. Tamarit, Nat. Commun., 2019, 10, 1803.
30 A. Aznar, P. Lloveras, M. Barrio, P. Negrier, A. Planes, L. Mañosa,
N. D. Mathur, X. Moya and J.-L. Tamarit, J. Mater. Chem. A, 2020, 8,
639–647.
31 E. Stern-Taulats, A. Planes, P. Lloveras, M. Barrio, J.-L. Tamarit,
S. Pramanick, S. Majumdar, C. Frontera and L. Mañosa, Phys. Rev. B:
Condens. Matter Mater. Phys., 2014, 89, 214105.
32 A. Aznar, P. Lloveras, M. Romanini, M. Barrio, J.-L. Tamarit,
C. Cazorla, D. Errandonea, N. D. Mathur, A. Planes, X. Moya and
L. Mañosa, Nat. Commun., 2017, 8, 1851.
33 S. P. Vallone, A. N. Tantillo, A. M. dos Santos, J. J. Molaison,
R. Kulmaczewski, A. Chapoy, P. Ahmadi, M. A. Halcrow and
K. G. Sandeman, Adv. Mater., 2019, 31, 1807334.
34 P. Lloveras, E. Stern-Taulats, M. Barrio, J. L. Tamarit, S. Crossley,
W. Li, V. Pomjakushin, A. Planes, L. Mañosa, N. D. Mathur and
X. Moya, Nat. Commun., 2015, 6, 8801.
35 H. Meng, B. Li, W. Ren and Z. Zhang, Phys. Lett. A, 2013, 377,
567–571.
36 Y. Liu, G. Zhang, Q. Li, L. Bellaiche, J. F. Scott, B. Dkhil and
Q. Wang, Phys. Rev. B, 2016, 94, 214113.
37 E. Stern-Taulats, T. Castán, L. Mañosa, A. Planes, N. D. Mathur and
X. Moya, MRS Bull., 2018, 43, 295–299.
Chem. Commun., 2020, 56, 10054--10057 | 10057