pubs.acs.

org/crystal Communication

Two-Dimensional Organic−Inorganic Hybrid Materials with

Dielectric Switching and Photoluminescence Properties
Qiang-Qiang Jia, Liang Tong, Meng-Meng Lun, Da-Wei Fu,* Tie Zhang,* and Hai-Feng Lu*
Cite This: Cryst. Growth Des. 2022, 22, 2799−2805 Read Online

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Layered 2D organic−inorganic halide perovskites

have attracted comprehensive scientific attention due to their
excellent dielectric, ferroelectric, and photophysical properties.
Downloaded via SUNGKYUNKWAN UNIV on June 26, 2024 at 06:59:32 (UTC).

However, most of the reported crystal compounds only possess a

single performance. Here, we report two new layered 2D organic−
inorganic halide perovskites: [BA-PbBr4] (Prv-1) and [MACH-
PbI4] (Prv-2) (BA = 1-butylamine, MACH = cyclohexanemethyl-
amine). Both compounds (with crystal structures) show switchable
phase transitions at 390 and 350 K, respectively. Shockingly,
[MACH-PbI4] reveals a high photoluminescence quantum yield of
up to 16.3% with the replacement of the halogen and organic
cation (Br → I, BA → MACH). In addition, the experimental data
and calculated results suggest that both compounds could be used
as band gap semiconductors. In brief, this work might provide new strategies for the exploration of dielectric and ferroelectric
functional materials.

Introduction. Organic−inorganic hybrid materials1−11 have
attracted considerable attention because of their flexible
structure and remarkable properties, such as photovoltaic,12
ferroelectric13−16 and. piezoelectric,17 and nonlinear optical
(NLO) properties.18−20 Among them, layered two-dimensional
(2D) organic−inorganic halide perovskites21−23 (as an
emerging semiconducting materials, they possess a strong
quantum confinement effect to achieve high PLQYs and,
moreover, photochromism can also be adjusted by halogen)
have widespread applications in solar cells,24,25 light emitting
diodes (LEDs),26−28 and photodetectors.29−31
Two-dimensional layered organic−inorganic halide perov-
skite materials exhibit good structural stability,32,33 photo-
voltaic/electric properties,34−37 and ferroelectricity based on
quantum confinement effects and flexible compositions. Some
of the above perovskite materials can be applied as semi-
conductors38−41 because of their appropriate band gap value.
Some of them show tunable dielectric behaviors because of
dynamic cation-induced reversible structural phase transi-
tions.42,43 The dielectric switching property of these kinds of
materials is very important in that it might promote the
exploration and design of multifunctional materials with
multiple switching response properties. Notably, most proper-
ties44 of the materials are mainly contributed by the inorganic
network while different organic cations could also lead to
completely distinct properties.45−47 At present, although the
reported materials have excellent properties, there are still
deficiencies. Sun’s group reported a 2D organic−inorganic
hybrid perovskite, (N-(3-aminopropyl)imidazole)PbCl4,48
whose color rendering index (CRI) was as much as 93;
however, its photoluminescence quantum yield (PLQY) was
less than 1%. In addition, their group also obtained a hybrid
perovskite, (2-methyl-1,5-diaminopentane)PbBr4;49 although it
had highly efficient white-light emission, the PLQY was only
about 3%. In addition, Zhao’s group reported a manganese-
doped two-dimensional chiral alloyed perovskite (containing
(PEA)2PbBr4),50 which exhibited a photoluminescent color
transition from blue to pink (achieving a change in the light
color). However, the photoluminescence quantum yield had a
certain loss.
Because of the deficiencies in the reported materials, in this
work we have synthesized two halide perovskite materials ([BA-
PbBr4] (Prv-1) and [MACH-PbI4] (Prv-2))51 via halogen
substitution (Br → I) and cation replacement (BA →
MACH).52−57 Both compounds exhibit a reversible phase
transition; in addition, Prv-2 has a photoluminescence effect.
Therefore, both compounds are potential dielectric switching
and luminescent materials.
Experimental Section. Materials and Methods. All
chemical reagents were purchased from commercial channels
Received: February 12, 2022
Revised: April 2, 2022
Published: April 6, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acs.cgd.2c00183

2799 Cryst. Growth Des. 2022, 22, 2799−2805
Crystal Growth & Design
Figure 1. (a) Stacked structures of Prv-1 at 300 and 400 K. (b) Stacked structures of Prv-2 at 300 and 365 K. (c) Ordered structure and dynamic
disordered structure of two cations for the LTP and HTP. (d) Hirshfeld surfaces and 2D-fingerprint plots.
and used without further purification. Dielectric constants were
recorded on a Tonghui TH2828A instrument at frequencies of
5 kHz, 10 kHz, 100 kHz, and 1 MHz and a measured AC
voltage of 1 V. Differential scanning calorimetry (DSC) was
measured on a NETZSCH DSC 3500 instrument by heating
and cooling at a rate of 20 K/min under a nitrogen atmosphere.
Thermogravimetric analysis (TGA) was carried out on a
NETZSCH STA 2500 instrument under a nitrogen atmosphere
with a heating rate of 20 K/min from room temperature (RT)
to 1100 K. UV−near-infrared−visible (UV-NIR-vis) spectra
were obtained on a Cary RF 6000 instrument, and the
fluorescence was determined on an FLS 9801 instrument.
Crystallographic Data Collection and Refinement. Crys-
tallographic structure factors were obtained with a Bruker D8
SMART SPEX-III instrument with a multiscan mode (Mo Kα
radiation, λ = 0.71073 Å) under 300 K and the required
temperature. Empirical absorption correction was adopted to
correct collected data on the basis of the SADABS program (I >
2σ(I) (ω = 1/[σ2(Fo2) + (P)2 ± P], where P = (Fo2 + 2Fc2)/3)).
The SHELXLE program was used to analysis the crystal
structure on the basis of direct and least-squares methods.
Anisotropy and geometric positioning of all atoms were refined
with OLEX 2 software. The bond lengths and angles in the
structure were calculated and measured with a DIAMOND or
MERCURY instrument. The final structure factors and
refinement data of Prv-1 and Prv-2 are given in Table S1.
Synthetic Procedures. Prv-1 and Prv-2 were obtained via the
reactions of PbBr2 and butylamine (BA) and of PbI2 and
cyclohexylmethylamine (MACH), respectively. PbBr2 (380 mg,
1.05 mmol) and butylamine (150 mg, 2 mmol) were mixed in
20 mL of a 40−45% HBr solution. The suspension was stirred
for 30 min at 100 °C, and then colorless block crystals were
collected by cooling slowly (about 2 K/day); and the yield was
67%. For Prv-2, PbI2 instead of PbBr2 and cyclohexylmethyl-
amine (MACH) instead of butylamine (BA) were used; the
pubs.acs.org/crystal Communication
other synthesis operations were same as those ofr Prv-1. Orange
crystals were collected with a yield of 59% (based on Pb). Mp:
236 °C (Prv-1), 257 °C (Prv-2).
Results and Discussion. Crystal Structures of Com-
pounds. Variable-temperature single-crystal X-ray diffraction
(SCXRD) was used to determine the structure of Prv-1 at 300
and 400 K. Usually, the low-temperature phase (LTP) is
considered to be the phase that is below the phase transition
point and the high-temperature phase (HTP) is the phase that
is above the phase transition point. Interestingly, the LTP and
HTP structures (Figure 1a) of Prv-1 both crystallize in a
centrosymmetric space group. At 300 K, Prv-1 crystallizes in the
orthorhombic crystal system and Pbca space group with a =
8.3447(9) Å, b = 8.2206(10) Å, and c = 27.628(3) Å. According
to the structural characteristics, a traditional 2D organic−
inorganic hybrid perovskite structure (A2BX4; A = cation(+), B
= transition-metal ion (M2+), and X = halogen atom) is adopted
by Prv-1 (Figure S1), in which A is an organic amine cation
(BAH+) supporting a 2D [PbBr4]2− layer network inside the
unit cell, B is both a point-sharing twist PbBr6 octahedron at the
1/8 vertex of the unit cell and also is a PbBr6 octahedron at the
1/4 edge. The BA cations (Figure 1c), located in the center of
the open cavities made up of PbBr6 octahedral units, are
ordered completely and connected to the [PbBr4]2− layer by
the weak hydrogen bond forces between the top amino groups
and Br atoms. Meanwhile, the free movement of the BA cations
is unaffected by the weak interactions. Therefore, Prv-1
crystallizes in the Cmca space group with a = 29.192(8) Å, b
= 8.291(2) Å, and c = 8.289(2) Å above 395 K. The structure
characteristics of HTP and LTP both belong to a 2D layered
perovskite type. Although the inorganic network is not changed
significantly, the BA cation (Figure 1c) exhibits an obvious
disorder on rotation by 180° around the center long axis.
Regardless of whether Prv-1 exists in the LTP or HTP, all bond
angles and lengths are within the normal range. Some of the
2800 https://doi.org/10.1021/acs.cgd.2c00183
Cryst. Growth Des. 2022, 22, 2799−2805
Crystal Growth & Design
Figure 2. (a) DSC curve of Prv-1. (b) DSC curve of Prv-2. (c) Dielectric curve of Prv-1 at 1 MHz. (d) Dielectric curve of Prv-2 at 1 MHz.
important bond lengths and angles for Prv-1 are given in Table
S2.
A pure crystal of Prv-2 was selected for a single-crystal X-ray
diffraction analysis. The structure data (Figure 1b) suggest that
the LTP (300 K) of Prv-2 crystallizes in the monoclinic crystal
system and the P21/c space group with a = 17.107(4) Å, b =
8.7364(16) Å, c = 8.73732(17) Å, and β = 100.611(6)°. In
comparison with the structural parameters (under 100 K) in the
reported literature,51 the higher temperature (at 300 K) makes
the molecular motion more intense and the unit cell parameters
are slightly different (a = 16.515(0) Å → 17.107(4) Å, b =
8.652(0) Å → 8.7364(16) Å, c = 8.764(0) Å → 8.7372(17) Å,
and β = 99.05(0)° → 100.611(6)°). Interestingly, the Prv-2
growth pattern is very similar to that of Prv-1 in that the organic
cation (MACH) is surrounded by cavities created by the open
PbI6 octahedra and connected by a hydrogen bond (N−H···I).
The distances between hydrogen and iodine are 2.739 and
2.767 Å, respectively. Meanwhile, the slightly deformed
octahedron [PbI6] was connected to others by a method of
point sharing and the organic cations are embedded in open
holes in the inorganic framework (Figure S2). At a higher
temperature (365 K), the structure of Prv-2 became
orthorhombic in the Cmca space group with a = 34.104(14)
Å, b = 8.732(3) Å, and c = 8.705(4) Å. When the organic phase
transition occurs, the cations undergo a transition from ordered
to 2-fold disordered; meanwhile, the arrangement of octahedral
units in the inorganic framework is also more ordered. Dynamic
organic cations (order−disorder) lead to the occurrence of
mainly a phase transition; however, the inorganic network
shows just a slight structural modification. As illustrated in
Figure 1c, the same 2-fold symmetry operation occurred on the
organic cations MACH and BA. Such a remarkable change
revealed a structural phase transition.
As demonstrated in Figure 1d, hydrogen-bond interactions
come from H atoms of amino groups and halogen atoms in the
inorganic network, which are shown in red in the Hirshfeld
surface, the distances between the inner (di) and outer (de)
nearest atoms of Prv-1 and Prv-2 are about 1.48 and 1.69 Å, and
pubs.acs.org/crystal Communication
the percentages of the corresponding forces (N−H···X, X = Br,
I) are 36.9% and 30.6%, respectively. The strength of the force
and the difference in percentages of two compounds could
prove that the phase transition temperature of Prv-1 (390 K) is
higher than that of Prv-2 (350 K).
DSC and Dielectric Analysis. To demonstrate that the
crystal structure had undergone a reversible phase transition
process, DSC and dielectric tests were performed. The DSC
curves show in Figure 2a,b that a pair of remarkable thermal
peaks are observed at 387.2 and 380.1 K in the heating/cooling
process, indicating that both Prv-1 and Prv-2 undergo a phase
transition triggered by the temperature. By a deep analysis of
the DSC curves, the detailed entropy changes of Prv-1 and Prv-
2 value were calculated to be ca. 12.57 and ca. 1.22 J K−1 mol−1,
respectively, by the Boltzmann equation (ΔS = R ln N). This
further proves that the phase transition is triggered by the
temperature. In the temperature-dependent dielectric constant
measurements (at 1 MHz), two obvious dielectric anomalies
(Figure 2a) are found at around 390 K in the heating/cooling
process. The value (ε′, real part of the dielectric constant) of
Prv-1 suddenly jumps from ca. 7.0 to ca. 9.5 at around 390 K
(LTP → HTP). When the sample is cooled, the ε′ sharply
drops from ca. 8.1 to ca. 7.5 (HTP → LTP). The reversible
dielectric anomalies suggest that Prv-1 undergoes a reversible
phase transition. The similarly reversible dielectric anomaly
signals are found in the temperature-dependent dielectric
constant measurements (at 1 MHz) of Prv-2, which also prove
that Prv-2 undergoes a reversible phase transition. This is
consistent with the DSC results (for both Prv-1 and Prv-2). The
frequency dependences of the dielectric constant (500 Hz, 1
kHz, 5 kHz, 10 kHz and 100 kHz) are recorded in Figure S4.
The results show that the value of ε′ (of both Prv-1 and Prv-2)
decreases with an increase in the frequency, which indicates the
frequency dependence of the dielectric constant (ε′, real part).
In addition, to verify the dielectric switching stability of the two
perovskite materials, multiple reversible dielectric cycles were
recorded (Figure S5). The results indicate that both materials
maintain a good stability of the dielectric constant during
2801 https://doi.org/10.1021/acs.cgd.2c00183
Cryst. Growth Des. 2022, 22, 2799−2805
Crystal Growth & Design pubs.acs.org/crystal Communication

Figure 3. (a) Photoluminescence schematic. (b) Luminous physical images of powder samples of Prv-1 and Prv-2. (c) Normalized maximum
excitation and emission spectra of Prv-1 and Prv-2. (d) PL decay data of Prv-2 where the blue points are raw data and the red line is the fitting curve.
(e) CIE coordinates of Prv-1 and Prv-2.

Figure 4. (a) UV-NIR-vis absorption spectra of Prv-1 and Prv-2. (b) Band structure of Prv-1. (c) Band structure of Prv-2. (d) Optical band gaps of
Prv-1 and Prv-2 from the Tauc equation. (e) Partial densities of state of Prv-1. (f) Partial densities of state of Prv-2.

multiple switching processes between high and low dielectric
states. On the basis of the above data, although the dielectric
switching properties of the two compounds in this work might
not be competitive in comparison with some special
2802
structure,58,59 the good dielectric stability of the two
compounds might still make them potential candidates in the
field of reversible dielectric switches. This might provide a
possible strategy for the design and and fabrication of
https://doi.org/10.1021/acs.cgd.2c00183
Cryst. Growth Des. 2022, 22, 2799−2805
Crystal Growth & Design
multifunctional materials with stable dielectric and luminescent
properties.
Optical Properties. The photoluminescence (PL) is mainly
excited by energetic ultraviolet light (Figure 3a), and materials
with a photoluminescent behavior might be applied in the light-
emitting diode (LED) field. Maximum excitation and emission
wavelengths were recorded with the use of a 445 nm optical
filter. In combination with UV-NIR-vis absorption spectrosco-
py (Figure S6), as shown in Figure 4a, the UV spectra of Prv-1
and Prv-2 exhibit broad UV absorption peaks at 375 and 345
nm and the photoluminescence spectra (Figure 3c) reveal
broad and tall emission bands at 460 and 540 nm, respectively.
In addition, Figure 3e shows that the chromaticity coordinates
(CIE) of PLE of Prv-1 and Prv-2 are (0.16, 0.06) and (0.21,
0.76), respectively. It spans the entire blue-green light color
zone from the blue-violet light of Prv-1 to the single green light
of Prv-2. From measurements, the photoluminescence quantum
yield (PLQY) of Prv-2 reached 16.3%; such a high quantum
yield is rarely seen in 2D lead halide perovskites in comparison
to those reported previously. Most importantly, the powdered
crystals of Prv-2 are capable of emitting emerald light under a
UV lamp at 365 nm (Figure 3b); however, Prv-1 does not
possess this interesting property. According to reports,60,61 in
comparison to 2D hybrids, 1D hybrids might show higher
vibrational degrees of freedom and polarization with photo-
excitation. Thus, the broad-band emission was enhanced with a
large Stokes shift. This might explain why Prv-1 (2D hybrids,
containing [PbBr4], with Stokes shift as small as ca. 90 nm) in
this work did not have an obvious luminescence property. For
Prv-2, the Stokes shift (obtained from Figure 3c) was ca. 200
nm. That value is large enough to achieve a luminescence
property. In a further analysis of the optical properties,
photoluminescence lifetime decay data Figure 3d show that
the short lifetime is 1.30 ns (τ1) with a percentage of 93.36%
(α1) and the long lifetime is 10.99 ns (τ2) with a percentage of
6.64% (α2), respectively. According to the formula τ = τ1α1 +
τ2α2, the calculated final lifetime is 2.76 ns (τ). This could signal
potential applications in the field of luminescence. In addition,
the synthesized sample has good stability under long-term UV
irradiation.
To clarify the reasons for the different properties of the two
compounds, optical band gaps and theoretical band gaps were
recorded and revealed. The optical band gap is obtained
through the UV-NIR-vis spectrum and calculated by the Tauc
equation. The theoretical band gap was determined with
Materials Studio software and the CASTEP program. UV-NIR-
vis spectra (Figure 4a) demonstrated that the maximum
absorption wavelength of Prv-1 is cut off at about 400 nm;
however, the maximum absorption wavelength of Prv-2 was still
at 510 nm and the optical band gaps (Figure 4d) of the two
compounds were considered to be 3.10 and 2.43 eV,
respectively. The band gap is in the normal range in comparison
to those reported previously. In addition, it can be seen (Figure
4b,c) that the band structure was obtained via the valence band
maximum (VBM) and conduction band minimum (CBM).
The VBM and CBM of the above polymers both belong to
special positions in the mutual space and are both characteristic
of direct band gap semiconductors with theoretical band gaps of
2.580 and 2.032 eV, respectively. In addition, as illustrated in
Figure 4e,f, the energy structure is mainly contributed by
halogen and lead(II) in the inorganic network (Pb-s, Pb-p, Pb-
d; Br-s, Br-p, Br-d; I-s, I-p, I-d). Consequently, both Prv-1 and
Prv-2 have good semiconductor properties.
pubs.acs.org/crystal Communication
Conclusions. In summary, two 2D organic−inorganic
hybrid materials ([BA-PbBr4] and [MACH-PbI4]) were
successfully obtained via the design of an inorganic framework
and organic cations. Prv-1 and Prv-2 both have high phase
transition temperatures (390 and 350 K, respectively). The
phase transition of the two compounds is attributed to the
reorientation of organic cations (BA and MACH); meanwhile,
the high PLQY of Prv-2 is due to the 2D layer characteristics of
the Wannier-type excitons with strong exciton binding energy.
Interestingly, Prv-2 showed a photoluminescence effect with a
high photoluminescence quantum yield of up to 16.3%. By a
combination of the experimental data with the calculated
theoretical results, the above two compounds are shown to be
direct band gap broad-band semiconductors. The materials in
this work show potential applications as multifunctional
materials in the fields of dielectric switches and LEDs.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.cgd.2c00183.
Crystallographic data and structural refinement details of
the compounds, selected bond lengths and angles of the
compounds, UV and fluorescence spectra, and thermog-
ravimetry and derivative thermogravimetry analyses
(TG-DTG) (PDF)
Accession Codes
CCDC 2125993 and 2132425−2132427 contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge via www.ccdc.cam.ac.uk/data_request/
cif, or by emailing data_request@ccdc.cam.ac.uk, or by
contacting The Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
■ AUTHOR INFORMATION
Corresponding Authors
Da-Wei Fu − Institute for Science and Applications of
Molecular Ferroelectrics, Key Laboratory of the Ministry of
Education for Advanced Catalysis Materials, Zhejiang
Normal University, Jinhua 321004, People’s Republic of
China; Ordered Matter Science Research Center, Jiangsu Key
Laboratory for Science and Applications of Molecular
Ferroelectrics, Southeast University, Nanjing 211189, People’s
Republic of China; orcid.org/0000-0003-4371-097X;
Email: dawei@zjnu.edu.cn
Tie Zhang − Ordered Matter Science Research Center, Jiangsu
Key Laboratory for Science and Applications of Molecular
Ferroelectrics, Southeast University, Nanjing 211189, People’s
Republic of China; Email: 230198852@seu.edu.cn
Hai-Feng Lu − Institute for Science and Applications of
Molecular Ferroelectrics, Key Laboratory of the Ministry of
Education for Advanced Catalysis Materials, Zhejiang
Normal University, Jinhua 321004, People’s Republic of
China; Email: luhaifeng@zjnu.edu.cn
Authors
Qiang-Qiang Jia − Institute for Science and Applications of
Molecular Ferroelectrics, Key Laboratory of the Ministry of
Education for Advanced Catalysis Materials, Zhejiang
Normal University, Jinhua 321004, People’s Republic of
China
2803 https://doi.org/10.1021/acs.cgd.2c00183
Cryst. Growth Des. 2022, 22, 2799−2805
Crystal Growth & Design
Liang Tong − School of Environment and Chemical
Engineering, Jiangsu University of Science and Technology,
Zhenjiang 212002, People’s Republic of China
Meng-Meng Lun − Ordered Matter Science Research Center,
Jiangsu Key Laboratory for Science and Applications of
Molecular Ferroelectrics, Southeast University, Nanjing
211189, People’s Republic of China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.cgd.2c00183
Author Contributions
Q.-Q.J. synthesized, characterized, and determined the single-
crystal structure of the perovskite materials. L.T. performed the
calculations and analyzed the band structure. M.-M.L.
measured the solid fluorescence excitation−emission wave-
length and decay lifetime. D.-W.F. provided suggestions for
research. T.Z. performed the characterization of the two
compounds. H.-F.L. designed and directed this work. All
authors contributed to the work in the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by the Natural Science
Foundation of Zhejiang Province (LZ20B010001) and the
National Natural Science Foundation of China (grant
21991141).
■
REFERENCES
(1) Ai, Y.; Sun, R.; Zeng, Y. L.; Liu, J. C.; Tang, Y. Y.; Wang, B. W.;
Wang, Z.; Gao, S.; Xiong, R. G. Coexistence of magnetic and electric
orderings in a divalent Cr2+-based multiaxial molecular ferroelectric.
Chem. Sci. 2021, 12, 9742−9747.
(2) Chen, X. G.; Song, X. J.; Zhang, Z. X.; Zhang, H. Y.; Pan, Q.; Yao,
J.; You, Y. M.; Xiong, R. G. Confinement-Driven Ferroelectricity in a
Two-Dimensional Hybrid Lead Iodide Perovskite. J. Am. Chem. Soc.
2020, 142, 10212−10218.
(3) Liu, J. C.; Liao, W. Q.; Li, P. F.; Tang, Y. Y.; Chen, X. G.; Song, X.
J.; Zhang, H. Y.; Zhang, Y.; You, Y. M.; Xiong, R. G. A Molecular
Thermochromic Ferroelectric. Angew. Chem., Int. Ed. 2020, 59, 3495−
3499.
(4) Mu, X.; Xu, L.; Xu, Y. Y.; Zhang, H. Y.; Xiong, R. G. High-
temperature enantiomeric azobenzene-based photoisomerized piezo-
electrics: 4-(phenyldiazenyl)anilinium) d- and l-tartrate. Mater. Chem.
Front. 2021, 5, 8371−8379.
(5) Xu, X. L.; Xiao, L. B.; Zhao, J.; Pan, B. K.; Li, J.; Liao, W. Q.;
Xiong, R. G.; Zou, G. F. Molecular Ferroelectrics-Driven High-
Performance Perovskite Solar Cells. Angew. Chem., Int. Ed. 2020, 59,
19974−19982.
(6) Zhang, H. Y.; Zhang, Z. X.; Chen, X. G.; Song, X. J.; Zhang, Y.;
Xiong, R. G. Large Electrostrictive Coefficient in a Two-Dimensional
Hybrid Perovskite Ferroelectric. J. Am. Chem. Soc. 2021, 143, 1664−
1672.
(7) Zhang, Z. X.; Zhang, H. Y.; Zhang, W.; Chen, X. G.; Wang, H.;
Xiong, R. G. Organometallic-Based Hybrid Perovskite Piezoelectrics
with a Narrow Band Gap. J. Am. Chem. Soc. 2020, 142, 17787−17794.
(8) Wang, P. H.; Yu, C. M.; Yu, X. Q.; Wang, M. S.; Guo, G. C. UV-
vis/X-ray/thermo-induced synthesis and UV-SWIR photoresponsive
property of a mixed-valence viologen molybdate semiconductor. Chem.
Commun. 2021, 57, 5550−5553.
(9) Li, J. Y.; Wang, C. F.; Wu, H.; Liu, L.; Xu, Q. L.; Ye, S. Y.; Tong,
L.; Chen, X.; Gao, Q.; Hou, Y. L.; Wang, F. M.; Tang, J.; Chen, L. Z.;
Zhang, Y. Eco-Friendly and Highly Efficient Light-Emission Ferro-
electric Scintillators by Precise Molecular Design. Adv. Funct. Mater.
2021, 31, 2170258.
pubs.acs.org/crystal Communication
(10) Li, J. Y.; Xu, Q. L.; Ye, S. Y.; Tong, L.; Chen, X.; Chen, L. Z. A
multiaxial molecular ferroelectric with record high TC designed by
intermolecular interaction modulation. Chem. Commun. 2021, 57,
943−946.
(11) Fu, D.; Xin, J.; He, Y.; Wu, S.; Zhang, X.; Zhang, X. M.; Luo, J.
Chirality-Dependent Second-Order Nonlinear Optical Effect in 1D
Organic-Inorganic Hybrid Perovskite Bulk Single Crystal. Angew.
Chem., Int. Ed. 2021, 60, 20021−20026.
(12) Capitaine, A.; Sciacca, B. Monocrystalline Methylammonium
Lead Halide Perovskite Materials for Photovoltaics. Adv. Mater. 2021,
33, 2102588.
(13) Li, G. P.; Lu, S. Q.; Chen, X.; Liao, W. Q.; Tang, Y. Y.; Xiong, R.
G. A Three-Dimensional M3AB-Type Hybrid Organic-Inorganic
Antiperovskite Ferroelectric: [C3H7FN]3[SnCl6]Cl. Chem. - Eur. J.
2019, 25, 16625−16629.
(14) Ji, C.; Sun, Z.; Zeb, A.; Liu, S.; Zhang, J.; Hong, M.; Luo, J.
Bandgap Narrowing of Lead-Free Perovskite-Type Hybrids for Visible-
Light-Absorbing Ferroelectric Semiconductors. J. Phys. Chem. Lett.
2017, 8, 2012−2018.
(15) Wu, Y.; Jiang, H.; Jiao, S.; Li, D.; Gao, Z.; Niu, B.; Wu, D.; Chen,
S.; Cai, H. L.; Wu, X. Chiral Zn-Based Organic-Inorganic Hybrid
Ferroelectrics with Large Polarization and Luminescence. Adv. Opt.
Mater. 2022, 10, 2101905.
(16) Fu, D. W.; Gao, J. X.; Huang, P. Z.; Ren, R. Y.; Shao, T.; Han, L.
J.; Liu, J.; Gong, J. M. Observation of Transition from Ferroelasticity to
Ferroelectricity by Solvent Selective Effect in Anilinium Bromide.
Angew. Chem., Int. Ed. 2021, 60, 8198−8202.
(17) Zhang, H. Y.; Chen, X. G.; Tang, Y. Y.; Liao, W. Q.; Di, F. F.;
Mu, X.; Peng, H.; Xiong, R. G. PFM (piezoresponse force
microscopy)-aided design for molecular ferroelectrics. Chem. Soc.
Rev. 2021, 50, 8248−8278.
(18) Gao, J. X.; Zhang, W. Y.; Wu, Z. G.; Zheng, Y. X.; Fu, D. W.
Enantiomorphic Perovskite Ferroelectrics with Circularly Polarized
Luminescence. J. Am. Chem. Soc. 2020, 142, 4756−4761.
(19) Li, S. L.; Xu, H. M.; Zhang, Y.; Yang, W.; Qi, Z.; Zhang, J.;
Zhang, X. M. A Photochromic Zinc-Viologen Framework with a High-
Contrast Nonlinear Optical Switchable Behavior. Cryst. Growth Des.
2021, 21, 5752−5759.
(20) Xie, Y.; Zheng, J.; Zheng, K.; Liu, Q.; Duan, J.; Chen, W.; Shao,
S.; Cai, H. High-Temperature Switchable Nonlinear Optical and
Dielectric Material Revealed by Molecular Modification. Chem. Mater.
2021, 33, 3081−3086.
(21) Shi, C.; Ye, L.; Gong, Z. X.; Ma, J. J.; Wang, Q. W.; Jiang, J. Y.;
Hua, M. M.; Wang, C. F.; Yu, H.; Zhang, Y.; Ye, H. Y. Two-
Dimensional Organic-Inorganic Hybrid Rare-Earth Double Perovskite
Ferroelectrics. J. Am. Chem. Soc. 2020, 142, 545−551.
(22) Liao, W. Q.; Zhang, Y.; Hu, C. L.; Mao, J. G.; Ye, H. Y.; Li, P. F.;
Huang, S. D.; Xiong, R. G. A lead-halide perovskite molecular
ferroelectric semiconductor. Nat. Commun. 2015, 6, 7338−7347.
(23) Su, C. Y.; Lun, M. M.; Chen, Y. D.; Zhou, Y. C.; Zhang, Z. X.;
Chen, M.; Huang, P. Z.; Fu, D. W.; Zhang, Y. Hybrid Optical-Electrical
Perovskite Can Be a Ferroelastic Semiconductor. CCS Chem. 2021, 3,
2021−2031.
(24) Zhao, R. Y.; Liu, G. N.; Liu, Q. S.; Niu, P. F.; Xu, R. D.; Wang, Z.
H.; Wei, T. H.; Zhang, J.; Sun, Y. Q.; Li, C. (3-Phenylpyridin-1-ium)
SbI4: Coulomb Interaction-Assembled Lead-free Hybrid Perovskite-
like Semiconductor. Cryst. Growth Des. 2020, 20, 1009−1015.
(25) Li, H.; Meng, F.; Malliakas, C. D.; Liu, Z.; Chung, D. Y.;
Wessels, B.; Kanatzidis, M. G. Mercury Chalcohalide Semiconductor
Hg3Se2Br2 for Hard Radiation Detection. Cryst. Growth Des. 2016, 16,
6446−6453.
(26) Yang, C.; Liu, X.; Teng, C.; Cheng, X.; Liang, F.; Wu, Q.
Hierarchical molecular design of high-performance infrared nonlinear
Ag2HgI4 material by defect engineering strategy. Mater. Today Phys.
2021, 19, 100432.
(27) Wu, Q.; Yang, C.; Liu, X.; Ma, J.; Liang, F.; Du, Y.
Dimensionality reduction made high-performance mid-infrared non-
linear halide crystal. Mater. Today Phys. 2021, 21, 100569.
2804 https://doi.org/10.1021/acs.cgd.2c00183
Cryst. Growth Des. 2022, 22, 2799−2805
Crystal Growth & Design
(28) Fu, D. W.; Gao, J. X.; He, W. H.; Huang, X. Q.; Liu, Y. H.; Ai, Y.
High-Tc Enantiomeric Ferroelectrics Based on Homochiral Dabco-
derivatives (Dabco = 1,4-Diazabicyclo[2.2.2]octane). Angew. Chem.
Int. Ed. 2020, 59, 17477−17481.
(29) Xie, Y. F.; Ai, Y.; Zeng, Y. L.; He, W. H.; Huang, X. Q.; Fu, D.
W.; Gao, Ji. X.; Chen, X. G.; Tang, Y. Y. The Soft Molecular
Polycrystalline Ferroelectric Realized by Fluorination Effect. J. Am.
Chem. Soc. 2020, 142, 12486−12492.
(30) Luo, Y. Y.; Zhang, Z. X.; Su, C. Y.; Zhang, W. Y.; Shi, P. P.; Ye,
Q.; Fu, D. W. Tunable optoelectronic response multifunctional
materials: exploring switching and photoluminescence integrated in
flexible thin films/crystals. J. Mater. Chem. C 2020, 8, 7089−7095.
(31) Li, J.; Xu, C.; Zhang, W. Y.; Shi, P. P.; Ye, Q.; Fu, D. W. Smart
and efficient opto-electronic dual response material based on two-
dimensional perovskite crystal/thin film. J. Mater. Chem. C 2020, 8,
1953−1961.
(32) Jiang, H.; Sun, C.; Yu, C. M.; Wang, M. S.; Guo, G. C.
Broadband Photoresponsive Bismuth Halide Hybrid Semiconductors
Built with π-Stacked Photoactive Polycyclic Viologen. Inorg. Chem.
2021, 60, 5538−5544.
(33) Hua, L.; Chen, H.; Han, S.; Xu, H.; Lu, L.; Tang, L.; Wang, B.;
Luo, J.; Sun, Z. 2D Hybrid perovskite incorporating cage-confined
secondary ammonium cations toward effective photodetection. Chem.
Commun. 2022, 58, 561−564.
(34) Yang, T.; Li, Y.; Han, S.; Liu, Y.; Xu, Z.; Li, M.; Wang, J.; Ma, Y.;
Luo, J.; Sun, Z. Exploiting two-dimensional hybrid perovskites
incorporating secondary amines for high-performance array photo-
detection. J. Mater. Chem. C 2020, 8, 12848−12853.
(35) Zheng, Y.; Xu, J.; Bu, X. H. 1D Chiral Lead Halide Perovskites
with Superior Second-Order Optical Nonlinearity. Adv. Opt. Mater.
2022, 10, 2101545.
(36) Wu, Y.; Fan, W.; Gao, Z.; Tang, Z.; Lei, L.; Sun, X.; Li, Y.; Cai,
H. L.; Wu, X. New photoluminescence hybrid perovskites with
ultrahigh photoluminescence quantum yield and ultrahigh thermo-
stability temperature up to 600 K. Nano Energy. 2020, 77, 105170.
(37) Su, C.; Yao, Y.; Zhang, Z.; Wang, Y.; Chen, M.; Huang, P.;
Zhang, Y.; Qiao, W.; Fu, D. The construction of a two-dimensional
organic-inorganic hybrid double perovskite ferroelastic with high Tc
and narrow band gap. Chem. Sci. 2022, DOI: 10.1039/D1SC07045B.
(38) Mao, L.; Wu, Y.; Stoumpos, C. C.; Wasielewski, M. R.;
Kanatzidis, M. G. White-Light Emission and Structural Distortion in
New Corrugated Two-Dimensional Lead Bromide Perovskites. J. Am.
Chem. Soc. 2017, 139, 5210−5215.
(39) Manser, J. S.; Christians, J. A.; Kamat, P. V. Intriguing
Optoelectronic Properties of Metal Halide Perovskites. Chem. Rev.
2016, 116, 12956−13008.
(40) Sun, C.; Xu, G.; Jiang, X.-M.; Wang, G.-E.; Guo, P.-Y.; Wang,
M.-S.; Guo, G.-C. Design Strategy for Improving Optical and Electrical
Properties and Stability of Lead-Halide Semiconductors. J. Am. Chem.
Soc. 2018, 140, 2805−2811.
(41) Li, H. H.; Wang, C. F.; Wu, Y. X.; Jiang, F.; Shi, C.; Ye, H. Y.;
Zhang, Y. Halogen substitution regulates the phase transition
temperature and band gap of semiconductor compounds. Chem.
Commun. 2020, 56, 1697−1700.
(42) Jiang, F.; Wang, C.-F.; Wu, Y.-X.; Li, H.-H.; Shi, C.; Ye, H.-Y.;
Zhang, Y. Nonlinear Optical and Photoluminescence Bistable
Responses Accompanied by Tunable Dielectric Behaviors in Crown
Inclusions. J. Phys. Chem. C 2020, 124, 5796−5801.
(43) Chen, X. X.; Liu, D. X.; Gong, Y. P.; Wang, S. S.; Zhang, W. X.;
Chen, X. M. Above-Room-Temperature Ferroelastic Phase Tran-
sitions in Two Tetrafluoroborate-Based Hexagonal Molecular Perov-
skites. Inorg. Chem. 2022, 61, 2219−2226.
(44) Wang, J.; Zhang, T.; Zhang, Z. X.; Su, C. Y.; Zhang, Y.; Fu, D.
W. Methylation Design Strategy to Trigger a Dual Dielectric Switch
and Improve the Phase Transition Temperature. Inorg. Chem. 2020,
59, 16635−16643.
(45) Liu, Y. T.; He, L.; Shi, P. P.; Ye, Q.; Fu, D. W. A one-
dimensional switchable dielectric material with Pd uptake function:
[(CH2)3NH2S]2BiCl5. Chem. Commun. 2020, 56, 13764−13767.
pubs.acs.org/crystal Communication
(46) Zeng, Y.; Hu, C. L.; Xu, W. J.; Zeng, T. W.; Zhu, Z. X.; Chen, X.
X.; Liu, D. X.; Chen, Y. J.; Zhang, Y. B.; Zhang, W. X.; Chen, X. M. An
Exceptional Thermally Induced Four-State Nonlinear Optical Switch
Arising from Stepwise Molecular Dynamic Changes in a New Hybrid
Salt. Angew. Chem., Int. Ed. 2022, 134, e202110082.
(47) Xu, W. J.; Romanyuk, K.; Zeng, Y.; Ushakov, A.; Shur, V.;
Tselev, A.; Zhang, W. X.; Chen, X. M.; Kholkin, A.; Rocha, J. Statics
and dynamics of ferroelectric domains in molecular multiaxial
ferroelectric (Me3NOH)2[KCo(CN)6]. J. Mater. Chem. C 2021, 9,
10741−10748.
(48) Wu, Z.; Ji, C.; Sun, Z.; Wang, S.; Zhao, S.; Zhang, W.; Li, L.;
Luo, J. Broadband white-light emission with a high color rendering
index in a two-dimensional organic-inorganic hybrid perovskite. J.
Mater. Chem. C 2018, 6, 1171−1175.
(49) Wang, S.; Yao, Y.; Kong, J.; Zhao, S.; Sun, Z.; Wu, Z.; Li, L.; Luo,
J. Highly efficient white-light emission in a polar two-dimensional
hybrid perovskite. Chem. Commun. 2018, 54, 4053−4056.
(50) Wang, C.; Ma, L.; Wang, S.; Zhao, G. Efficient Photo-
luminescence of Manganese-Doped Two-Dimensional Chiral Alloyed
Perovskites. J. Phys. Chem. Lett. 2021, 12, 12129−12134.
(51) Li, Z.; Najeeb, M. A.; Alves, L.; Sherman, A. Z.; Shekar, V.; Cruz
Parrilla, P.; Pendleton, I. M.; Wang, W.; Nega, P. W.; Zeller, M.;
Schrier, J.; Norquist, A. J.; Chan, E. M. Robot-Accelerated Perovskite
Investigation and Discovery. Chem. Mater. 2020, 32, 5650−5663.
(52) Zhang, Y.; Liao, W. Q.; Fu, D. W.; Ye, H. Y.; Chen, Z. N.; Xiong,
R. G. Highly Efficient Red-Light Emission in An Organic-Inorganic
Hybrid Ferroelectric: (Pyrrolidinium)MnCl3. J. Am. Chem. Soc. 2015,
137, 4928−4931.
(53) Qi, Z.; Gao, H.; Yang, X.; Chen, Y.; Zhang, F. Q.; Qu, M.; Li, S.
L.; Zhang, X. M. A One-Dimensional Broadband Emissive Hybrid
Lead Iodide with Face-Sharing PbI6 Octahedral Chains. Inorg. Chem.
2021, 60, 15136−15140.
(54) Qi, Z.; Chen, Y.; Guo, Y.; Yang, X.; Gao, H.; Zhou, G.; Li, S. L.;
Zhang, X. M. Highly efficient self-trapped exciton emission in a one-
dimensional face-shared hybrid lead bromide. Chem. Commun. 2021,
57, 2495−2498.
(55) Tang, L.; Chen, H.; Ma, Y.; Liu, Y.; Hua, L.; Lu, L.; Wang, B.;
Han, S.; Sun, Z.; Luo, J. A bilayered two-dimensional hybrid perovskite
with a cage-templated secondary cation for high efficiency photo-
detection. Inorg. Chem. Front. 2022, 9, 637.
(56) Sanni, A. M.; Lavan, S. N.; Avramenko, A.; Rabuffetti, F. A.;
Suescun, L.; Rury, A. S. Room-Temperature Broadband Light
Emission from Hybrid Lead Iodide Perovskite-Like Quantum Wells:
Terahertz Spectroscopic Investigation of Metastable Defects. J. Phys.
Chem. Lett. 2019, 10, 1653−1662.
(57) Torubaev, Y.; Skabitsky, I.; Lyssenko, K. A. Stages of
Kitaigorodsky Aufbau Principle Detached in the Cocrystals of
Cp2MX2 (M = Ti, Zr; X = Cl, Br, I) with σ- and π-Hole Donors.
Cryst. Growth Des. 2022, 22, 1244−1252.
(58) Liu, L. R.; Miao, L. P.; Han, X. B.; Zhang, W. Hydrogen-Bonded
Molecular Crystals Showing Terminal-Group Triggered Phase
Transitions and Dielectric Responses. Cryst. Growth Des. 2021, 21,
5342−5348.
(59) Tao, K. W.; Han, S. G.; Ji, C. M.; Liu, X. T.; Wu, Z. Y.; Zhang, J.;
Luo, J. H.; Sun, Z. H. Structural Phase Transition and Switchable
Dielectric Properties of a Unique Two-Dimensional Organic-Inorganic
Hybrid Perovskite Compound [C6H11NH2CH3]4Pb3I10. Cryst.
Growth Des. 2018, 18, 7316−7322.
(60) Lin, H.; Zhou, C.; Neu, J.; Zhou, Y.; Han, D.; Chen, S.; Worku,
M.; Chaaban, M.; Lee, S.; Berkwits, E.; Siegrist, T.; Du, M. H.; Ma, B.
Bulk Assembly of Corrugated 1D Metal Halides with Broadband
Yellow Emission. Adv. Op.t Mater. 2019, 7, 1801474.
(61) Qi, Z.; Chen, Y.; Guo, Y.; Yang, X.; Gao, H.; Zhou, G.; Li, S. L.;
Zhang, X. M. Highly efficient self-trapped exciton emission in a one-
dimensional face-shared hybrid lead bromide. Chem. Commun. 2021,
57, 2495−2498.
2805 https://doi.org/10.1021/acs.cgd.2c00183
Cryst. Growth Des. 2022, 22, 2799−2805