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An unprecedented hexagonal double perovskite

organic–inorganic hybrid ferroelastic material:
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Cite this: Chem. Commun., 2021,

57, 6292 (piperidinium)2[KBiCl6]†
Received 19th April 2021,
Accepted 22nd May 2021 Qian-Ru Meng,a Wei-Jian Xu,ab Wang-Hua Hu,a Hui Ye,a Xiao-Xian Chen,a
Wei Yuan,a Wei-Xiong Zhang *a and Xiao-Ming Chena
DOI: 10.1039/d1cc02085d

rsc.li/chemcomm

An unprecedented A2MIMIIIX6-type double perovskite adopting a ferroelastic materials. For instance, Fu et al. reported a hybrid
fully hexagonal BaNiO3-type structure, (piperidinium)2[KBiCl6], hexagonal perovskite, (Me3PCH2OH)[CdBr3], exhibiting a
undergoes a 2/mF1% ferroelastic phase transition at 285 K with a 6/mmmFmmm ferroelastic phase transition at 339 K with a
spontaneous strain of 0.0615, arising from the order–disorder spontaneous strain of 0.0646.25 Besides judiciously choosing
transition of organic cations together with the synchronous dis- A-site organic cations, an effectively supplementary way to
placement of inorganic chains. modulate the properties of halide perovskite hybrids is by using
two components to alternately occupy the B sites, typically,
Ferroelastic materials exhibit unique mechanical properties using M+ and M3+ metal ions to replace two B-site M2+ ions to
such as spontaneous strain, strain–stress hysteresis, and yield double perovskite hybrids with a general chemical for-
domain conversion, and thus have potential for employing in mula of A2MIMIIIX6. Such a strategy has made success in
a wide range of applications such as piezoelectric sensors, yielding some halide double perovskite hybrids being under
mechanical switches, and multiple-state memories.1–8 As spotlight in the photovoltaic community and ferroelectro-
proposed by Aizu, a ferroelastic material should undergo a chemistry, in which M+ is K+, Na+, Li+, Ag+, or Cu+ and M3+ is
phase transition belonging to one of the 94 species of ferroe- Ga3+, Tl3+, In3+, Bi3+, or Sb3+. Nevertheless, the employed A-site
lastic phase transitions.9,10 The ferroelastic domain, which cation is usually a small organic cation such as CH3NH3+,
results from the symmetry reduction from a paraelastic to a NH2CHNH2+, and C4H11N+, and the resultant perovskite
ferroelastic phase, is an important ingredient in functionalities hybrids either possess a cubic prototype structure with a
of ferroelastic materials.11–13 Recently, the exploration of novel three-dimensional coordination framework or a layered struc-
ferroelastic materials has been extended to organic–inorganic ture with a two-dimensional coordination framework.26–33
hybrid crystals, which generally have more mechanical flexi- Halide hexagonal double perovskite hybrids with one-
bility than pure inorganic ones, benefiting from the potential dimensional coordination chains, as an important branch of
large responses to mechanical stress caused by order–disorder perovskite structure, have unique structural flexibility to host
transitions or conformation changes of flexible organic interesting structural transitions especially the ferroelectric
cations.14–22 and ferroelastic ones, however, to the best of our knowledge,
In particular, ABX3-type halide perovskite hybrids,23 in have not been documented to date.
which A usually is an organic cation, B is a metal ion, and X Aiming to construct a halide hexagonal double perovskite,
is a halogen anion,6,24 have attracted increasing interest due to we choose relatively large and flexible cyclic ammonium
their potential to act as not only optoelectric materials but also cations,34 e.g., piperidinium cation (C5H12N+), to assemble with
two halide salts, e.g., KCl and BiCl3. Our efforts have success-
a
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry,
fully yielded a new A2MIMIIIX6-type hexagonal double perovs-
School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China. kite, (C5H12N)2[KBiCl6] (1), which adopts a fully hexagonal
E-mail: [email protected] BaNiO3-type structure and undergoes a reversible order–disor-
b
Department of Chemistry & CICECO-Aveiro Institute of Materials, der ferroelastic transition with a spontaneous strain of 0.0615.
University of Aveiro, Aveiro 3810-193, Portugal
Herein, we present the structural details and the underlying
† Electronic supplementary information (ESI) available: Single-crystal structures,
thermogravimetric analysis, and powder X-ray diffraction patterns. CCDC
ferroelastic mechanism of this unprecedented hexagonal
2072112 and 2072113. For ESI and crystallographic data in CIF or other electronic double perovskite ferroelastic, as disclosed by means of
format see DOI: 10.1039/d1cc02085d thermal analysis, variable-temperature single-crystal/powder

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Fig. 1 (a) DSC curves of 1. (b) Temperature dependence of the dielectric

constants (e 0 ) for 1 measured at a frequency of 50–250 kHz.

X-ray diffraction, dielectric measurements, polarization micro-

scopy and Hirshfeld surface analyses.
1 was obtained by slow evaporation of a mixed aqueous
solution of C5H11NHCl, KCl, and BiCl3 in a molar ratio of
2 : 1 : 1. Thermogravimetric analysis showed that 1 is stable up
to 463 K under a N2 flow (Fig. S3, ESI†). As shown in differential
scanning calorimetry (DSC) curves (Fig. 1a), a pair of endo- Fig. 2 Asymmetric unit and the 3D crystal packing viewed along the
thermic/exothermic peaks was observed at 285/282 K (Tc) in c-axis in (a and c) the LTP at 228 K and (b and d) the HTP at 298 K.
Symmetric codes: (A) x, 1  y, z, (B) x, y, 1  z, (C) x, y, 1  z, (D) x, y,
heating and cooling runs, respectively, indicating a reversible z, (E) x, y, z, (F) x, y, z, and (G) x, y, 1 + z.
phase transition for 1. The thermal hysteresis of 3 K, together
with a significant enthalpy change (DH) of 5.3 kJ mol1,
suggested a first-order phase transition. For convenience, we 2.644(2)–2.773(2) Å. The resultant KCl6 and BiCl6 octahedra are
labeled the phases at above and below Tc as the high- alternatively linked by sharing two opposite faces to form a one-
temperature phase (HTP) and low-temperature phase (LTP), dimensional coordination chain extending along the c-axis. Two
respectively. crystallographically independent ordered organic cations form
Such a phase transition was also reflected in a step-like N–H  Cl weak hydrogen-bonds to the inorganic chain with
change of the dielectric constant (e 0 ). As shown in Fig. 1b, the e 0 N  Cl distances of 3.349(4)–3.492(4) Å, and they act as A-site
value is ca. 5.03 at 210 K, gradually increases to 5.27 at 270 K, cations to occupy the interchain space to complete a hexagonal
and then rapidly increases to 5.94 at 295 K. Such step-like double perovskite structure. It is worth noting that, different from
dielectric responses implied an order–disorder dynamic transi- the recently-reported Cs2AgCrCl6 adopting a Ba2NiTeO6-type struc-
tion of the polar guest cation in 1. In addition, the phase ture with mixed equal-proportion corner- and face-sharing
transition was further confirmed using variable-temperature octahedra,35 1 is the first example of a halide double perovskite
powder X-ray diffraction (PXRD) patterns (Fig. S2, ESI†). The adopting a fully hexagonal prototype structure or otherwise called
experimental PXRD patterns recorded at 298 K and 288 K of 1 a BaNiO3-type structure exhibiting only face-sharing octahedra.
match well with the simulated pattern at 298 K. When the In the HTP, its structure belongs to the centrosymmetric
temperature was decreased to 283 K and 243 K, the main monoclinic space group C2/m with cell parameters of
diffraction peak shifted to a higher angle by 0.151, and three a = 17.4817(9) Å, b = 7.7663(4) Å, c = 7.7181(3) Å,
additional peaks were observed at 12.51, 16.51, and 20.81, b = 91.632(4)1, and V = 1047.45(9) Å3. The asymmetric unit in
respectively, implying a lower symmetric lattice for the LTP. the HTP is quartered when compared with that in the LTP. Both
To understand the mechanism of this structural phase transi- K+ and Bi3+ locate on special positions with a site occupancy of
tion, in situ variable-temperature single-crystal X-ray diffraction 0.25, and the K–Cl and Bi–Cl bond lengths vary in a narrow
was performed at 228 and 298 K for probing the structural details range of 3.1342(1)–3.1562(2) Å and 2.6992(9)–2.7040(1) Å,
of the LTP and HTP, respectively. Structural analyses revealed that respectively. The organic cation locates on a mirror plane
1 crystallizes in a typical hexagonal double perovskite structure. In perpendicular to the b axis and becomes disordered on this
detail, the crystal structure measured at 228 K (LTP) belongs to the plane (Fig. 2b and d).
triclinic space group P1% , with cell parameters of a = 9.5493(6) Å, During the phase transition from C2/m (HTP) to P1% (LTP),
b = 14.0781(8) Å, c = 7.7339(5) Å, a = 86.029(5)1, b = 89.324(5)1, the number of symmetry elements varies from 4 (E, C2, i, and
g = 79.883(5)1, and V = 1021.09(1) Å3 (Table S1, ESI†). The sh) to 2 (E and i), and such symmetry breaking belongs to a
asymmetric unit of the LTP contains two C5H12N+ moieties and ferroelastic phase transition with an Aizu notation of 2/mF1% .9 By
one [KBiCl6] moiety (Fig. 2a). Each K+ is coordinated to 6 Cl with using variable-temperature polarization microscopy on a single
a K–Cl bond length of 3.110(2)–3.180(2) Å, and each Bi3+ crystal viewed perpendicular to the (201% ) plane in a temperature
is coordinated to 6 Cl with a Bi–Cl bond length of range of 273–298 K, we investigated the variation of the

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Fig. 3 Polarized microscopy observations on a single crystal of 1 perpendicular to the (201% ) plane at different temperatures.

ferroelastic domain to confirm the ferroelasticity. At first, as (Me4P)4[Mn(SCN)6] (0.102),37 but is close to or larger than
shown in Fig. 3a, no ferroelastic domain structure exists in the those in halide hexagonal perovskite hybrids, such as
paraelastic phase at 298 K. When the temperature was (Me3PCH2OH)[CdBr3] (0.0646),25 (C5H12N)[CdCl3] (0.040),38 and
decreased to the vicinity of a critical temperature of 283 K, (N-methylpyrrolidinium)[MnCl3] (0.045).39 These results implied
stripe patterns appeared on the crystal surface immediately that such large spontaneous strain in 1 should be highly asso-
(Fig. 3b), corresponding to the ferroelastic domains in two anti- ciated with not only the order–disorder dynamic transition of the
parallel orientation states predicted for such a 2/mF1% ferroelas- flexible organic cation but also the double perovskite structure
tic species.36 Upon further cooling, these ferroelastic domains constructed by judiciously introducing monovalent K+ and triva-
became more clear, and the revolution was completed at 273 K lent Bi3+ into the inorganic chain.
(Fig. 3d). Upon reversely heating up to 283 K (Fig. 3e), the To understand the role of organic cations in the change of
ferroelastic domains gradually faded away and then disap- intermolecular interactions during the phase transition, the
peared completely to recover the initial phase at 298 K Hirshfeld surfaces and fingerprints are analyzed for organic
(Fig. 3f). Such appearance and disappearance of the cations (Fig. 4). As indicated by the red spots on Hirshfeld
multi-domain structure could be repeated by further several surfaces, for both the LTP and HTP, the main molecular interac-
cooling–heating cycles (see Movie S1, ESI†), well confirming a tions between organic cations and inorganic chains are the
reversible ferroelastic transition for 1. N–H  Cl weak hydrogen-bonds. The smallest (di, de) pair of the
For the present 2/mF1% species, the spontaneous strain tensor intermolecular H  Cl short contact is (0.86 Å, 1.47 Å) and (0.96 Å,
is given as:10 1.58 Å) for two crystallographically independent cations in the
2 3 LTP, respectively, and becomes (1.10 Å, 1.63 Å) for the crystal-
e11 e12 e13
lographically independent cations in the HTP. This fact indicated
eij ¼ 4 0 e22 e23 5
that accompanied by the dynamic transition of organic cations
0 0 e33
from the disordered state in the HTP to the ordered state in the
LTP, the HCl short contact is slightly strengthened and hence
Based on the aforementioned cell parameters and a necessary induces the synergistic interchain displacements at the ab plane
conversion matrix on the cell of HTP to match the structures at as well as the interchain slide along the c-axis.
228 K and 298 K (for details, see ESI†), the total spontaneous In summary, by judiciously assembling piperidinium
strain for the present ferroelastic transition was estimated as: cations with KCl and BiCl3, we obtained an unprecedented
sffiffiffiffiffiffiffiffiffiffiffiffiffi halide hexagonal double perovskite hybrid crystal adopting a
X ffi
ess ¼ eij2 ¼ 0:0615 BaNiO3-type structure, i.e., 1, which undergoes a ferroelastic
i;j phase transition at around 285 K. Moreover, by investigating
the structural details and the weak interactions between the
organic cations and the inorganic chains, we found that such
Such a value is smaller than those in some ferroelastic hexagonal double perovskite hybrid crystals have an advantage
hybrids consisting of discrete coordination entities such as of inducing a relatively large structural deformation and a

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