pubs.acs.

org/crystal Article

Mechanical Properties of a New Hybrid Inorganic−Organic

Framework: A Nanoindentation, High-Pressure X‑ray Diffraction,
and Computational Study
Li-Jun Ji, Zhi-Gang Li, Li-Yuan Dong, Ying Zhang, Tian-Meng Guo, Fei-Fei Gao, Guo-Qiang Feng,*
and Wei Li*
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sı Supporting Information

ABSTRACT: The comprehensive mechanical properties of a new

synthesized 3D hybrid inorganic−organic framework (TPrA)-
Cu2(dca)5 (TPrA+ = N(C3H7)4+, tetrapropylammonium; dca− =
N(CN)2−, dicyanamide) have been studied via experimental
approaches and first-principles calculations. The nanoindentation
test demonstrates that Young’s moduli (E) and the hardness within
the 2D [Cu2(dca)4] layers are respectively 65 and 70% larger than
the direction normal to the 2D planes, and the framework of
(TPrA)Cu2(dca)5 is prone to cleavage along the 2D [Cu2(dca)4]
layers to lead to discrete displacement bursts in the initial loading
part of the load-indentation depth (P-h) curve of the <020>
direction. The bulk modulus of (TPrA)Cu2(dca)5 is 6.97 GPa within a pressure scope of 0 to 3.36 GPa, which is comparable to
those from porous MIL-47 and ZIF-8. The high anisotropy of Young’s moduli of 31.8 and the shear moduli of 45.0 provided via first-
principles calculations are an order of magnitude larger than those from many known porous and dense frameworks but close to
those of 2D hybrid systems. The broad range of Poisson’s ratio of (TPrA)Cu2(dca)5 indicates its very anisotropic response behavior
when under the uniaxial and shearing stress. The results of nanoindentation, synchrotron high-pressure X-ray diffraction, and first-
principles calculations synergistically indicate that the 3D architecture of (TPrA)Cu2(dca)5 has the potential to cleavage into 2D
nanosheets under the uniaxial or shearing stress. Further high-resolution microscopic characterization directly confirms the
successful exfoliation of the 3D framework of (TPrA)Cu2(dca)5 into 2D nanosheets via simple surfactant-free solvent-mediated
sonication and demonstrates that the (−102) plane is the cleavage plane.

■ INTRODUCTION
Hybrid inorganic−organic framework materials are a family of
single-phase compounds in the crystalline state, which are
formed by linking inorganic metal (M) clusters or ions with
multitopic organic bridges (L) to construct infinite arrange-
ments in an M-L-M connected manner in at least one
dimension.1 Over the past two decades, this family has drawn
increasing attention of researchers by their enormous chemical
and structural diversity, and a large number of researchers have
focused on creating exotic properties or combining unique
properties that existed in purely inorganic or organic
compounds by designing and synthesizing new structures.2
Now to date, the researchers have usually sorted the hybrid
frameworks into two main categories. One is nanoporous
coordination polymers known as metal−organic frameworks
(MOFs).3 Their novel structural natures such as ordered pore
structure, tailorable pore size, large specific surface area, and
ultrahigh porosity endow them with significant potential in
many practical applications.4 The other is dense hybrid
frameworks, the structures of which are more similar to those
of classical inorganic materials, showing semiconductivity and
multiferroic, optical, and magnetic properties in functional
devices which are traditionally dominated by inorganic or
organic materials.5
Although there have been a great large number of publications
aiming at designing new architectures and developing novel
functions,2,5 only a small amount of studies have been aimed at
understanding the mechanical behaviors which deserve more
attention. Because on the one hand, the framework structures
have to possess sufficient stiffness and resilience under the
mechanical loading to refrain from distortion, collapse, and
amorphization. On the other hand, functions such as
piezoluminescence and piezoelectricity are strongly dependent
on the elastic properties of the architectures.6 Motivated by the
Received: June 13, 2022
Revised: October 27, 2022
Published: November 7, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acs.cgd.2c00658

6984 Cryst. Growth Des. 2022, 22, 6984−6994
Crystal Growth & Design
ultimate goal of applying these promising frameworks into
practical applications, the mechanical response behavior of
many representative porous frameworks (i.e., ZIF-8 and MOF-
5) and layered molecular crystals, Omeprazole for instance, has
been extensively studied via nanoindentation and first-principles
calculations, and the important information including the
elasticity and plasticity, hardening and stiffness, and structural
evolution under stress has been reported.7−14 Furthermore, how
weak interactions and microscopic structural topology work on
the dynamic phenomena like the phase transition, phase
deformation, and elastic flexibility of 2D organic crystals have
been comprehensively studied.15,16 For instance, the π-stacking
and C−H···O belonging to weak interaction play a main role in
the loading-caused phase transition between the harder caffeine
and the softer 4-chloro-3-nitrobenzoic acid.15 Moreover,
significant mechanical responses like brittle fracture, plastic
bending, plastic shearing, elastic flexibility, and elastic bending
under mechanical deformation tests of layered organic crystals
are investigated.17−20 However, studies concerning the stress
and strain related behavior of Cu-based frameworks are few, the
structure−mechanical property relationship is not comprehen-
sive, and controlling and directing the mechanical behavior of
hybrid frameworks by using inorganic or organic building blocks
with different stiffness is still an issue.21,22
Hitherto, the two main categories of methods are widely
implied to prepare nanosheets for the MOF family. The first is a
top-down route referring to peeling the layers from their mother
bulks. Owing to the stiff covalent bonds within the layer and
fragile interactions among layers, the layered bulk MOFs (e.g.,
[Fe(bimX)2] (HBIMX = benzimidazole functionalized in the 5-
position, X = H, Cl, Br, CH3, or NH2)) can be cleaved into
nanosheets by approaches such as Scotchtape,23,24 sonica-
tion,25,26 intercalation,27,28 milling,29,30 and freeze−thaw.31,32
The second is a bottom-up route which means synthesizing the
MOF nanosheet by assembling the metal ions with organic
ligands. Both methods have long been considered and only can
be used to generate nanosheets from MOFs which originally
possess a layered structure. To further broaden the range of
available precursors and enrich their corresponding applications,
trying 3D MOFs as exfoliation sources is also a feasible way.
Herein, we concentrate on the mechanical properties of a new
synthesized 3D hybrid framework (TPrA)Cu2(dca)5. Specifi-
cally, we probed the elastic properties, plastic properties, and
high-pressure behaviors of this hybrid framework by nano-
indentation, first-principles calculation, and synchrotron high-
pressure X-ray diffraction (HP-XRD) approaches. Our results
give that the outstanding anisotropy of the mechanical
properties of this Cu-based 3D framework can be attributed to
the synergy of the rigid 2D [Cu2(dca)4] connectivity along the
<−102> direction and the sparse M-L-M bridges along <20−3>
directions which connect adjacent [Cu2(dca)4] layers to form a
3D architecture. Furthermore, scanning electron microscopy
(SEM), transmission electron microscopy (TEM), and atomic
force microscopy (AFM) characterization reveal that because
this 3D dense framework possesses prominent mechanical
anisotropy which is even much larger than some classic 2D
materials (Table S1), the (TPrA)Cu2(dca)5 can be piled into
nanosheets via simple surfactant-free solvent-mediated soni-
cation.
■ EXPERIMENTAL SECTION
Synthesis. All chemicals and solvents were purchased with reagent
grade and used as received. In the synthesis procedure, Cu(NO3)2·
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3H2O (2 mmol, 0.484 g) was dissolved in 15 mL of water and combined
with a mixture liquid of Na(dca) (dca− = N(CN)2−, dicyanamide) (6
mmol, 0.534 g) and (TPrA)Br (TPrA+ = N(C3H7)4+, tetrapropylam-
monium) (2 mmol, 0.532 g) in 15 mL water. Dark green crystals
appeared by slow evaporation after 3 weeks. Then the crystals were
manually picked up from the liquid, and their purity was validated by
powder X-ray diffraction (Figure S1). We collected the infrared spectra
in the range of 4000−400 cm−1 via a Bruker Vertex 70 FTIR
spectrometer equipment. FT-IR (KBr): ṽ = 3754 (w), 3659 (w), 3435
(m), 3124 (w), 3087 (w), 2979 (w), 2942 (w), 2884 (w), 2781 (w),
2398 (w), 2337 (m), 2311 (s), 2279 (s), 2195 (vs), 1633 (w), 1479
(w), 1458 (w), 1393 (m), 1352 (m), 1160 (w), 1101 (w), 1053 (w),
1031 (w), 1002 (w), 967 (w), 938 (w), 843 (w), 761 (w), 649 (w), 505
(m), 422 (w) cm−1. Elemental analysis was performed by using a Vario
Micro Cube elementar. The elemental analysis calcd (%) for
(TPrA)Cu2(dca)5 (Mr = 321.83): C 41.05, H 4.38, N 34.82; found:
C 41.02, H 4.19, N 34.74.
Single-Crystal X-ray Diffraction. We used a Rigaku XtalAB mini
diffractometer which was equipped with graphite monochromated Mo
Kα (λ = 0.71073 Å) to collect the single-crystal X-ray diffraction data. A
crystal with a dimension of 0.78 × 0.42 × 0.21 mm3 was affixed on a
glass fiber by glue and collected over the range of 2.606 to 29.579° (θ)
at 300 K. Data processing including reduction, face indexation, and
absorption corrections was performed by the CrysAlisPro33 program.
The structure was solved by the direct method and refined based on F2
by the full matrix least-squares method using a SHELX-9734 software
package. All nonhydrogen atoms were refined with anisotropic thermal
parameters. The positions of hydrogen atoms attached to nitrogen
atoms and carbon atoms were generated geometrically using a riding
model. The Olex235,36 software was used as an interface for the SHELX
program. The crystallographic parameters are summarized in Table S2,
the length of selected bonds and the selected angles are listed in Table
S3, and the asymmetric unit is shown in Figure S2. Crystallographic
data for the compound have been deposited at the Cambridge
Crystallographic Data Centre (Deposit no. 2083249) and can be
obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif.
Nanoindentation. The single crystals possessing a completeness
level of over 93% were selected via single-crystal X-ray diffraction by fast
collecting a sphere of data using an incremental scan method. Then
before doing the nanoindentation, the selected single crystal was firmly
affixed on iron stages. The experiments were operated on two natural
faces (010) and (−102) (Figure S3) by using a Berkovich diamond
nanoindenter with a three-sided pyramidal shape (Triboindenter of
Hysitron, Minneapolis, USA). The load (P) and displacement (h) of
tested single crystals were continuously monitored and recorded by the
equipment with a force resolution of 5 mN and a displacement
resolution of 0.2 nm. The tip radius of the indenter applied to indent the
crystals was about 100 nm. To access regions which are flat enough for
the experiment, we imaging the crystal surfaces by the same indenter tip
in AFM mode before doing the nanoindentation.37 The 10 × 10 μm2
regions with root mean square roughness (Rq, RMS roughness) below
30 nm were selected before each loading. Rq and average roughness Ra
were 6.8 and 6.2 nm respectively for the selected region in the (020)
plane (Figure 2b), and 15.8 and 8.9 nm respectively for the selected
region in the (−102) face (Figure 2c). The loading and unloading rates
were 0.5 mN/s, and the hold time at peak load was 10 s. We performed
seven indentations on each crystallographic face (Figure S4). To avoid
the elastic recovery of the residual impressions after indentation, we
captured the indentation impressions immediately after unloading by
AFM mode.
We used quasi-static mode to conduct the nanoindentation
experiments. The unloading stiffness (S) is established by the equation
S = dP/dh at the initial point of unloading. Therefore, we can find
Young’s modulus (E) and hardness (H) at the maximum depth of
penetration. As the fact that both the specimen and the indenter
undergo elastic deformation, according to eq 1, the reduced modulus
(Er) was used in analysis to explain it.
Er =
2
S
Ac
(1)
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Cryst. Growth Des. 2022, 22, 6984−6994
Crystal Growth & Design
Figure 1. Crystal structure of (TPrA)Cu2(dca)5 viewed along the b-axis (a) and c-axis (b), where TPrA+ is tetrapropylammonium and dca− is
dicyanamide. Color scheme: Cu2+, olive; C, light gray in dca− ligand and dark gray in TPrA+ cation; N, blue. The TPrA+ cations in (a) and hydrogen
atoms in (b) are omitted for clarity.
In eq 1, the Ac is the projected contact area under load, and β is a
constant which depends on the geometry of the indenter (β = 1.034 for
the Berkovich tip). Based on the Oliver−Pharr method,38,39 for a given
sample, its Young’s modulus can be extracted from the reduced
modulus according to eq 2:
1 1 vi2 1 vs2
= +
Er Ei Es (2)
In eq 2, E and v are Young’s modulus and Poisson’s ratio, respectively.
The subscripts i and s refer to the indenter and test material,
respectively. The indenter properties used in this study are Ei = 1141
GPa and vi = 0.07. The different faces of the single crystals were
assumed to possess isotropic elastic properties with vs = 0.3. The
hardness of a material is defined as its resistance to local plastic
deformation, and indentation hardness (H) thus can be determined
from the maximum indentation load (Pmax) and can be divided by the
contact area (Ac) according to eq 3:
Pmax
H=
Ac (3)
In eq 3, the contact area (Ac) is a function of the contact depth (hc),
Ac = f(hc). The contact depth can be determined from the P−h data by
using eq 4:
Pmax
hc = hmax
S (4)
where hmax is the maximum indentation depth and ε is a constant which
depends on the geometry of the indenter.
High-Pressure Synchrotron Powder X-ray Diffraction. We
performed the synchrotron HP-XRD characterizations by using the 4
W2 beamline in Beijing Synchrotron Radiation Facility (BSRF). The
wavelength of the X-ray beam is 0.61990 Å, and the X-ray beam was
focused into a spot with a size of 36 × 12 μm2 by Kirkpatrick−Baez
mirrors. We used the diamond anvil cells (DACs) to generate a
hydrostatic pressure, and their culet diameter is 400 μm. With the
increase of pressure from atmospheric pressure, all the diffraction peaks
move to high angles gradually, indicating the shrinkage of crystal
lattices. Nevertheless, when the pressure continually increased over the
threshold of 3.358 GPa, some weak diffraction peaks began to
disappear, which manifested the partial amorphous process of the
(TPrA)Cu2(dca)5 structure. To maintain the structural crystallinity, we
analyzed the high-pressure behaviors of (TPrA)Cu2(dca)5 in the range
of 0∼3.358 GPa. Crystals of (TPrA)Cu2(dca)5 were sufficiently ground
into powder and subsequently loaded with a few ruby balls in a cave of
about 200 μm diameter in a preindented stainless steel gasket with a
thickness of about 40 μm.40 Both the sample and ruby balls were sealed
in DACs with the silicone oil as the pressure-transmitting media at
room temperature. We calibrated the pressure in DACs by measuring
the fluorescence of the ruby balls.41 The Pilatus 2 M detector was used
to collect the diffraction patterns. The diffraction patterns then were
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integrated by the FIT2D software package.42 The lattice parameters of
the unit cell obtained from Le Bail fits are listed in Table S4.
First-Principles Calculation. Cambridge Sequential Total Energy
Package (CASTEP)43,44 was used to perform the first-principles
calculations. This energy package is based on plane-wave pseudo-
potential density functional theory (DFT).44 We developed the
function by using Perdew, Burke, and Ernzerhof in the generalized
gradient approximation (PBE-GGA)45 form to represent the exchange-
correlation energy. We employed the finite method to determine the
elastic constants of (TPrA)Cu2(dca)5.46 The energy cut-off was fixed at
400 eV, and the k-point mesh sampling scheme of Monkhorst-Pack was
set to 2 × 2 × 1 for geometry optimization, density of states, and elastic
constants.47 The crystal structure was optimized at 0 GPa through the
relaxation of both the lattice parameters and atomic positions. In
geometry optimization, the convergence criteria for energy, maximum
stress, maximum displacement, and maximum force were set as 10−5 eV
per atom, 0.05 GPa, 10−4 Å, and 0.005 eV Å−1, respectively. After
obtaining the elastic constants, the 3D distribution of Young’s modulus,
Poisson’s ratio, and shear modulus were calculated by the ELATE
program.48
Scanning Electron Microscopy. The nanosheets were exfoliated
by dispersing 1 mg powder of (TPrA)Cu2(dca)5 in 1 mL of isopropanol
and then sonicated for about 90 min (120 W, 40 kHz). The milky
suspension was centrifuged with a rate of 6000 r/min. The bottle
sediment including exfoliated nanosheets and incomplete exfoliated
bulks was dipped on a preheated clean silicon substrate. A layer of
conductive gold particles was coated on the surface of the sample after
the solvent completely evaporated. The sample then was imaged by
field-emission scanning electron microscopy (FESEM, Sigma 500,
Germany).
Atomic Force Microscopy. We used the Digital Instrument
Multimode SPM equipped with a BRUKER RTESPA-300 tip in the
tapping mode to image the surface topographies of samples and offer
the height profiles of nanosheets. The nanosheets were fabricated by
dispersing 0.1 mg of the (TPrA)Cu2(dca)5 powder in 5 mL of
isopropanol (20 mL cylindrical vial) and sonicated for about 90 min in a
the KQ3200DE ultrasonic cleaner. The power and frequency were fixed
at 120 W and 40 kHz, respectively. After the obtained milky suspension
was centrifuged with a rate of 4500 r/min, the vial was then kept still for
5 min, dipping the top suspension on a clean preheated silicon substrate
(1 × 1 cm2). The as-prepared nanosheets were scanned with a rate of
0.80 Hz when the residual solvent on the substrate was evaporated. The
resolution of the images was 512 × 512 pixel2. The operation point, P
gain, and integral gain were set as 0.153 V, 0.001, and 1000, respectively.
Transmission Electron Microscopy. The nanosheets used in this
experiment were prepared by dispersing 0.1 mg powder of (TPrA)-
Cu2(dca)5 in 1 mL of isopropanol. The above powder was sonicated for
about 90 min (120 W, 40 kHz). Droplets of the suspension were dipped
onto the holey carbon-coated Cu grids and evaporated in the air. We
operated the Titan 60−300 Cs Corrected transmission electron
microscope at 300 kV to capture the bright-field and high-resolution
TEM (HRTEM) images of nanosheets and used the JEM-2100
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Cryst. Growth Des. 2022, 22, 6984−6994
Crystal Growth & Design
Figure 2. (a) P−h curves normal to the (020) and (−102) planes of single crystals of (TPrA)Cu2(dca)5 measured with a Berkovich tip. (b, c) Typical
AFM height topology obtained from the residual indents corresponding to the P−h curves depicted in (a). Rq and Ra were 6.8 and 6.2 nm for the region
in (b) and 15.8 and 8.9 nm for the region in (c). Their cross-sectional profiles along the three designated directions are plotted in (d, e).
electron microscope at 200 kV to obtain the selected area electron
diffraction (SAED) pattern, because the nanosheets of (TPrA)-
Cu2(dca)5 were frail and easy to lose crystallinity within 15 s when
under the electron beam.
■ RESULTS AND DISCUSSION
Crystal Structure. (TPrA)Cu2(dca)5 (TPrA+ = N(C3H7)4+,
tetrapropylammonium; dca− = N(CN)2−, dicyanamide) crys-
tallizes in the orthorhombic space group Pbca with cell
parameters a = 13.9367(8), b = 16.4222(9), and c =
25.878(2) Å. The asymmetric unit of the structure is composed
of two Cu2+, five dca− ligands, and a TPrA+ guest. The Cu2+ ion
is five-coordinated in a pyramidal geometry by five dca− ligands.
The Cu−N distances are in the range of 1.970(3)−2.258(3) Å,
and the N−Cu−N angles lie in the range of 88.5(7)−174.7(3)°
(Figure S2, Tables S2−3). Each Cu1N5 polyhedron links two
Cu1N 5 polyhedrons along the b-axis and one Cu2N 5
polyhedron along <10−2> direction via three single dca−
linkers but links one Cu1N5 polyhedron along the a-axis via
double dca− ligands, while each Cu2N5 polyhedron bridges two
Cu2N5 polyhedrons along the b-axis by linking two single dca−
linkers and one Cu2N5 polyhedron along <10−2> direction by
one single dca− ligand. The inorganic CuN5 polyhedrons and
organic dca− linkers corporately form the infinite [Cu2(dca)4]
connectivity, and this connectivity extends approximately within
the (−102) plane to form a corrugated 2D layer. The adjacent
2D [Cu2(dca)4] layers are about 0.6 nm apart and bridged by the
tilt Cu1-dca−-Cu2 connectivity with a length of about 0.82 nm
along the <20−3> direction to produce a 3D [Cu2(dca)5]−
framework (Figure 1a). This anion framework is charge
balanced by the TPrA+ guest cations which are located in the
framework cavities, and the projections of the TPrA+ cations
along the b-axis are largely overlapped (Figure 1b). Further
examination suggests that the dca− ligands within 2D
[Cu2(dca)4] layers are highly flexed with the angle of C13−
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N7−C16 being about 119.5° and the distance of Cu-dca−-Cu
connectivity is about 0.71 nm, while the dca− linkers between
adjacent 2D [Cu2(dca)4] layers are stretched with an angle of
C20−N16−C22 of about 124.2° and the distance of Cu-dca−-
Cu connectivity is about 0.83 nm. The inspection above
indicates that the bonding strength within the 2D [Cu2(dca)4]
plane is much stronger than it is between [Cu2(dca)4] planes.
Moreover, the (−102) plane which is coincident with the 2D
[Cu2(dca)4] layer is the morphologically major face with the
largest interplanar spacing. Therefore, the (−102) has the lowest
attachment energy which is calculated via Bravais−Friedel−
Donnay−Harker (BFDH) theory.52 Hence, (−102) can be
considered as a facile slip plane for allowing intermittent flake
movement along the b-axis during mechanical loading. For most
2D structures, layer stacking via weak interactions is known to
allow sudden and collective slip to relax and accommodate the
loading stress imposed on the mechanically deformed
crystals.15,16,20
Nanoindentation Study. To elucidate the structural
stiffness of the 3D hybrid framework (TPrA)Cu2(dca)5, we
carried out nanoindentation measurements on the naturally
grown (020) and (−102) faces of the single crystals using a
sharp Berkovich tip in the quasi-static mode, and the maximum
load was set as 5 mN.49,50 The naturally grown two facets agree
well with the BFDH morphology calculated from Mercury
software. The representative load-indentation depth (P−h)
curves obtained on the two different faces are shown in Figures
2a and S4.
The P−h curves accomplished on the two natural facets are
different and exhibit significant residual depths upon complete
unloading, indicating that the two planes undergo significant
plastic deformation during the indentation. The (020) face
shows a smaller penetration depth (hmax) of about 478 nm as
compared to the (−102) face with a hmax of about 637 nm. The
high value of hmax for (−102) correlates well with its observed
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Cryst. Growth Des. 2022, 22, 6984−6994
Crystal Growth & Design
high plastic behavior and demonstrates its smaller hardness
(Figure 2c).
The loading segment of the P−h curve obtained on (−102) is
smooth, presenting a homogeneous plastic deformation. In
contrast, the loading part of the P−h curve on (020) presents
discrete displacement bursts (“pop-ins”). Such discrete events
signify intermittent plasticity instead of a continuous change.
The magnitudes of the displacement burst (hpop‑in) were found
to be 5.7, 8.1, 6.3, and 7.9 nm, respectively, which are 7 to 10
times interplanar d-spacing of the (020) facet (∼0.8 nm).51 The
“pop-ins” originate from the collective and sudden sliding of
multiple (−102) planes during indentation, because the 2D
[Cu2(dca)4] layers are oriented approximately parallel to the
indenter axis (b-axis) when indenting the (020) face, and the
Cu2−N15−C22−N16−C20−N12−Cu2 linkages which work
for binding the 2D layers together along the <20−3> direction
are broken although the strength of most coordination bonding
typically is of about 50 to 200 kJ mol−1, the shearing of the layers
consequently occurs to produce the bursts of displacements
(Figure 1a). In contrast, no “pop-ins” were observed on the
(−102) face when loading along the normal orientation of 2D
layers, such a phenomenon can be construed as the shrinkage of
soft organic (TPrA)+ cations which act as spacers to shorten the
interlayer distance persistently.
It is worth noting that the occurrence of “pop-ins” for 2D
hybrid frameworks is quite different from that in layered organic
crystals. For layered organic crystals, the “pop-ins” generally
appear and are more dominant in the direction normal to the
layers because of the microscopic elastic compression of the
layers followed by a sudden slippage upon reaching a critical load
applied by the indenter tip.15,16,20 In contrast, for hybrid and
inorganic structures, the indenter axis that is approximately
parallel to the layers often leads to obvious or more significant
displacement bursts than that normal to the layers. It arises from
the breakage of weak bonds between neighboring layers such as
van der Waals forces, hydrogen bonds, and covalent bonds
inducing shearing of layers.21 Such a correspondence was also
witnessed in 2D hybrid crystals such as Mn(C6H8O4)(H2O),
Cu3(H2O)2[O3PCH2CO2]2, and (TPrA)Cu(NO3)(dca)2.21,55
The AFM topography and cross-sectional profiles of indents
obtained from the (020) and (−102) faces are depicted in
Figure 2. Only one minor (about 165 nm above the original
surface) pile-up appears on one side of the residue impression
for the (020) plane (Figure 2b), while the more distinct “pile-
ups” (about 200, 286, and 495 nm above the original surface)
can be seen on all three edges of the indent for (−102) face by
applying the same load (Figure 2c). It can be seen that the pile-
up behavior is highly anisotropic, indicating the underlying 2D
layered structure and the quite distinct interactions between
intra- and interlayer. According to the microscopic crystal
structure nature of the (TPrA)Cu2(dca)5 framework, the
[Cu2(dca)4] layers are broken plastically under the sustain
increased loading stress normal to the (−102) plane, but the
broken fragments are hard to slip apart because of the
comprehensive obstruction of the Cu2−N15−C22−N16−
C20−N12−Cu2 covalent connectivity between layers, the
high overlap of TPrA+ cations within the (−102) plane, and
the electrostatic force between TPrA+ cations and the
[Cu2(dca)5]− framework. The significant amount of broken
cleavage plane ejects out of the edges around the indenter,
therefore, leading to the dramatic pile-ups of the (−102) plane.
In contrast, the oblique angle of the indentation direction from
the 2D [Cu2(dca)4] plane is responsible for the existence of pile-
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up merely on one side for the (020) face.55 It is noted that the
extensive pile-ups around the edge of the indentation can result
in the underestimation of the contact area (Ac) for isotropic
materials; therefore, Young’s modulus and hardness were
overestimated. For anisotropic crystals, researchers try to read
Ac directly from the residual indents at a fully unloaded state to
measure the degree of anisotropy more precisely. Then they
found that the recalculated E and H are still relatively lower
because of pile-ups, but the anisotropic ratios of E and H are
comparable with those obtained using the Oliver−Pharr
method.21,50
The average values of Young’s modulus (E) and hardness (H)
extracted from the P−h curves (Figure 2a) are 15.18(29) and
0.46(03) GPa for the (002) face, and 9.21(18) and 0.27(28)
GPa for the (−102) face, respectively, by using the Olive−Pharr
method in which the pile-up effects are not accounted for. The
ratio53,54 between the two planes in E and H is E(002):E(−102) =
1.65:1 and H(002):H(−102) = 1.7:1, respectively, giving a change in
the modulus of about 65%. The (020) face was found to have a
higher modulus, while the (−102)-oriented face was found to be
of lower modulus, indicating that the 2D [Cu2(dca)4] layers
which are bonded via covalent Cu2−N15−C22−N16−C20−
N12−Cu2 chains are relatively compliant when loaded along the
normal orientation ((−102) direction). According to the crystal
structure of the (TPrA)Cu 2 (dca)5 framework, the 2D
[Cu2(dca)4] layers are connected via a single type of chain
(Cu2−N15−C22−N16−C20−N12−Cu2) along the <20−3>
direction, and the length and the bending angle of this type of
chain are 0.83 nm and 124.2°, respectively. In contrast, the Cu2+
cations within layers are connected via three types of chains
(double Cu1-N6-C16-N7-C13-C2-Cu1 chains along the a-axis,
two Cu1-N3-C14-N5-C15-N4-Cu1 chains along the b-axis, and
single Cu1-N8-C17-N9-C18-N10-Cu2 along the <−102>
direction), and the lengths and bending angles of these three
types of the chain are about 7.1 nm and 119.5° for Cu1−N6−
C16−N7−C13−C2−Cu1, 0.81 nm and 122.1° for Cu1−N3−
C14−N5−C15−N4−Cu1, and 0.82 nm and 123.1° for Cu1−
N8−C17−N9−C18−N10−Cu2. It is obvious that the lengths
and bending angles of Cu-dca−-Cu chains within [Cu2(dca)4]
layers are smaller than that between layers. The chain-like ligand
with a shorter length and a smaller bending angle generally
possess stronger bonding strength and vice versa. Therefore, the
interlayer Cu-dca−-Cu chains are relatively weak and present
lower resistance against external compressive and shear stresses.
In contrast, the (020) face shows a higher modulus with a
magnitude about twice than that of the (−102) face. This is
because the indenter orientation for the (020) experiments is
approximately parallel to the 2D [Cu2(dca)4] layers, demon-
strating that the Cu-dca−-Cu chains within 2D planes are stiffer
and able to withstand a certain extent of elastic strains such as
translational and torsional motions of polyhedra, bond
stretching and bending, or combination of the above.50
High-Pressure Properties. The nanoindentation gives that
for the 3D (TPrA)Cu2(dca)5 framework, the bonds within 2D
[Cu2(dca)4] layers are significantly stiffer than that between
layers when they are under the external elastic strains. Thus, the
intralayer should be more compressible than the interlayer. To
quantitatively check this orientation-dependent compressibility
of (TPrA)Cu2(dca)5, the high-pressure synchrotron X-ray
diffraction measurements were performed under the hydrostatic
environment. The representative diffraction patterns collected
at 0, 1.82, and 3.36 GPa are shown in Figure S5a. It is clear that
with the increase of pressure, no new diffraction peaks appeared
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Crystal Growth & Design
during the compression process, and all the peaks move to high
angles gradually, demonstrating that there was no phase
transition, and the shrinkage of crystal lattices occurred due to
the shortened interatomic distances. Although some weak
diffraction peaks disappear, the crystallinity of the sample is
retained in the whole pressure range from ambient to 3.36
GPa,40,56 which is in significant contrast with the porous MOFs
that have a relatively low amorphization pressure threshold.10
Based on the cell parameters extracted from Le Bail fits at each
pressure (Table S3, Figure S5b), the compressibility of
interplanar spacings of (−102), (100), and (020) facets is
calculated via the Bragg diffraction formula with a magnitude of
about 9.7, 7.1, and 9.1%, respectively, within a pressure scope of
3.36 GPa. The maximum change in compressibility is about
37%, and it is clear that the (100) plane is the toughest. As
presented in Figure 1a, the Cu1N5 polyhedron links its nearest
neighbor Cu1N5 via double Cu1−N6−C16−N7−C13−C2−
Cu1 chains with the shortest chain length (7.1 nm) and smallest
chain bending angle (119.5°) to form unbroken loop-like
linkages oriented along the <100> direction. Such structural
nature not only adds extra stiffness to the 2D [Cu2(dca)4] layers,
but also leads to further anisotropy. As external hydrostatic
pressure was applied, the (100) facet was compressed along the
<100> direction, where the smallest compressibility was
obtained. By contrast, the (−102) and (020) faces have
relatively low compressibility. In contrast, the 2D [Cu2(dca)4]
layers lie in the (−102) plane which is bounded via the single
Cu2−N15−C22−N16−C20−N12−Cu2 chain with the longest
chain length (0.83 nm) and largest chain bending angle
(124.2°), and the (−102) face thus is more compliant and
presents largest compressibility. As depicted in Figure 1b, the
Cu1N5 polyhedron within 2D [Cu2(dca)4] layers extends the
two Cu1−N3−C14−N5−C15−N4−Cu1 chains along <020>
and <0−20> directions, respectively, to bridge the Cu1N5 with a
middle chain length (0.81 nm) and chain bending angle
(122.1°), explaining why the compressibility of (020) was found
to lie between those of the (−102) and (100). Moreover, we also
discuss the bulk modulus of the (TPrA)Cu2(dca)5, and the unit
cell volume decreases by 24.9% at 3.36 GPa (Figure 3). The
pressure−cell volume data were fitted by using the PASCal
software with the second-order Birch−Murnaghan equation.57
The fitted bulk modulus is 6.97 GPa lying in the range of values
for many known porous MOFs (∼5−30 GPa)53 but adopted a
nonporous structure with the large TPrA+ cation located in the
Figure 3. Evolution of unit cell volume as a function of pressure. The
experimental data with error bars are presented as dark gray dots, and
the second-order Birch−Mumaghan fitting curve obtained by using
PASCal is shown as a green line.
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cavities of the anion [Cu2(dca)5]− framework. This value is
significantly smaller than that of the dense stacked (Gua)[Zn-
(HCOO)3] (calc. 38.41 GPa)58 and metal-free (C4N2H12)-
[NH4I3·H2O]59 but comparable to that of porous MIL-47 (calc.
9.74 GPa),60 ZIF-8 (calc. 9.21 GPa),9 and MOF-5 (calc. 17.61
GPa),7 certifying its much softer nature in resistance to
hydrostatic compression.
First-Principles Calculations. To further understand the
comprehensive elastic properties of the framework (TPrA)-
Cu2(dca)5, its full elastic tensors were calculated based on the
optimized crystal structure at 0 GPa by using the DFT-GGA +
PBE method.61,62 For the orthorhombic system, the obtained
nine independent elastic constants and derived Young’s moduli
(E), shear moduli (G), and Poisson’s ratios (v) are listed in
Table 1. The theoretical values of E(002) and E(−102) extracted
from the above elastic
constants are 12.9 and 10.8 GPa, respectively, which is in good
agreement with the aforementioned nanoindentation results,
testifying to the rationality of the DFT elastic tensors. The bulk
modulus extracted from the matrix is 12.71 GPa, which is 5.73
GPa larger than the experimental synchrotron powder
diffraction value of 6.97 GPa. The two following factors are
response for the difference: (i) The DFT calculations were
performed at 0 K, while the high-pressure synchrotron powder
diffraction experiments were performed under ambient
conditions.63 (ii) The silicone oil solidifies at 2.0 GPa but
remains nearly quasi-hydrostatic in the pressure range which
would affect the experimental results.64,65 Accordingly, the
larger calculated values are expected, and the 1−6 GPa
difference is reasonable and common.40,65−67
In terms of Young’s modulus reflecting the ability of a given
material to resist uniaxial deformation, the highly distorted 3D
surface reflecting significant anisotropy is shown in Figure 4a,d.
E reaches the maxima along the <805> direction with a
magnitude of 14.6 GPa, and this direction approximately lies in
the (−102) plane which is along the rigid 2D [Cu2(dca)4]
connectivity plane. Thus this orientation exhibits the largest
stiffness. In addition, E reduces to the minima along the <011>
direction with the value of 0.5 GPa, which is attributed to the
collective influences including the staking manner of the 2D
[Cu2(dca)4] layer along the <020> direction via sparse and soft
dca− ligands and the staggered arrangement of soft TPrA+
cations along the c-axis. Notably, the anisotropy of E of
(TPrA)Cu2(dca)5 defined as the ratio AE = Emax/Emin is about
31.8, which is an order of magnitude larger than that of both
common porous frameworks like ZIF-8 (1.4)9 and MOF-5
(4.3)7 and dense framework like (C4N2H12)[NH4I3·H2O]
(2.2)59 and (Gua)[Zn(HCOO)3] (2.7),58 even significantly
larger than those of typical 2D materials, such as graphene
(28.4),68 black phosphorus (6.5),69 MoS2 (4.6),70 and
(Benzylammonium)2PbBr4 (4.9)71 (Table S1). As the out-
standing anisotropy of Young’s modulus always indicates an
extreme anisotropic bonding manner which is often seen in the
2D materials’ family, this feature of (TPrA)Cu 2 (dca) 5
accordingly indicates that this 3D hybrid framework could be
exfoliated into nanosheets like 2D structures via applying
uniaxial strain.
For a framework, the shear modulus reflects the resistant
ability to change in shape or angle. The 3D and 2D distribution
of shear modulus are presented in Figure 4b,e, respectively. The
G reaches the maximum value of 5.3 along the <−47−6>
direction when shearing the (−476) plane, while reaches the
minimum value of 0.1 along the <001> when shearing the (010)
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Crystal Growth & Design pubs.acs.org/crystal Article

Table 1. Elastic Constants and the Maximal and Minimal Values of Elastic Properties of (TPrA)Cu2(dca)5 and Other Typical 3D
Crystalsa
Cij (GPa)
elastic properties C11 C22 C33 C44 C55 C66 C12 C13 C23
(TPrA)Cu2(dca)5 32.74 20.96 16.39 0.12 4.71 2.03 16.20 15.76 8.29
E (GPa) G (GPa) v
Emax Emin AE Gmax Gmin AG vmax vmin Av K (GPa)
14.6 0.5 31.8 5.3 0.1 45.0 2.7 −1.7 6.97b
ZIF-89 3.9 2.7 1.4 1.4 0.9 1.5 0.6 0.3 2.0 9.21
MOF-57 21.3 4.9 4.3 8.2 1.7 4.8 0.8 0.09 8.9 17.6
(C4N2H12)[NH4I3·H2O]59 53.3 24.0 2.2 21.4 7.5 2.8 0.6 0.1 6.9 29.47
(Gua)[Zn(HCOO)3]58 70.9 26.6 2.7 24.8 11.0 2.3 0.8 0.1 6.0 31.82
a
All extremum values were derived by using the ELATE48 software. Anisotropy of X is defined as Ax = Xmax/Xmin. bExtracted from the high-pressure
synchrotron diffraction experiment.

Figure 4. 3D and 2D plots of Young’s modulus E (a, d), shear modulus G (b, e), and Poisson’s ratio v (c, f) of (TPrA)Cu2(dca)5. In (b, c), the
transparent outer layer and nontransparent inner layer represent the maximum values and minimum values, respectively. In (e, f), the blue line and red
line correspond to the maximum and minimum values, respectively.

plane. These values give rise to a remarkable anisotropic index
AG of 45, which is characterized as the ratio of Gmax/Gmin. This
anisotropic index is more than an order of magnitude higher
than it of both porous and dense frameworks listed in Table 1,
also significantly larger than it of prototypical 2D materials listed
in Table S1. This high shear anisotropy of (TPrA)Cu2(dca)5
indicates its structural instability under the shearing stress
although it is formed via strong coordinative and covalent bonds.
Turning attention to Poisson’s ratio (v), which is charac-
terized as the ratio of the transverse strain (εj) to the axial strain
(εi), v = −εj/εi. As shown in Figure 4c,f, the Poisson’s ratio is
maximized to 2.7 when stretched along the <924> direction,
giving rise to a lateral contraction along the <177> direction.
The Poisson’s ratio is minimized to −1.7, when loaded along the
<924> direction with a lateral expansion along <−233>
direction. Notably, the Poisson’s ratio ranges from −1.7 to
2.7, which is much wider than that of many well-known 3D
porous and dense materials, lying on either side of the value of
0.26, implying its significant anisotropy and between ductile and
brittle nature. This boundary feature is also verified by Pugh’s
criterion,72 according to which the K/G ratio of (TPrA)-
Cu2(dca)5 is in the range of 1.3−69.7, including the threshold
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value of 1.75, demonstrating that its boundary nature is between
ductile and brittle.
Liquid Exfoliation. From the above analysis of the crystal
structure−mechanical property relationship, we can know that
the 3D column-laminar framework (TPrA)Cu2(dca)5 is formed
via 2D [Cu2(dca)4] layers extending in the (−102) plane and 1D
chain-like Cu2−N15−C22−N16−C20−N12−Cu2 linkages
used to bound the adjacent layers. As the Cu-dca−-Cu linkages
of the intralayer show a shorter bonding distance and a smaller
bending angle than those of interlayer, the bonding strength of
2D [Cu2(dca)4] planes is significantly stronger than that
between layers. In this regard, it can be seen that the
nanoindentation and high-pressure behaviors are highly
anisotropic, demonstrating the underlying 2D layered structural
characteristics and the distinct interactions between the
intralayer and interlayer. For instance, the occurrence of “pop-
ins” on the (020) facet and the orientation-dependent pile-up
features in nanoindentation measurements collaboratively
indicate that the (−102) plane is prone to generate slippage
when the applied uniaxial stress is oriented parallel to the 2D
[Cu2(dca)4] planes. Further DFT calculations also indicate that
the anisotropy indexes are comparable to even larger than the
2D family, which manifests the structural instability of the 3D
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Crystal Growth & Design
Figure 5. AFM surface topographies (a) and the corresponding height profiles (b) of multilayered nanosheets. TEM bright-field image (c) of ethanol
exfoliated nanosheets supported on a holey copper mesh. HRTEM image (d) of the 2D nanosheets showing the crystal lattice, the inset is the SAED
pattern.
(TPrA)Cu2(dca)5 framework. Taking those into account, we
speculate that the (TPrA)Cu2(dca)5 could be exfoliated into 2D
nanosheets by simply applying uniaxial and shearing stress. As
the liquid phase exfoliation process contains both shearing and
uniaxial stresses along any orientation, we exfoliated this 3D
(TPrA)Cu2(dca)5 by simple surfactant-free solvent-mediated
sonication to confirm our conjecture. One milligram of well-
ground powder of the bulk crystals was dispersed in 1 mL of
isopropanol, then sonicating this mixture for a period of 90 min.
We performed SEM to examine the morphologies of these
products and get direct evidence of successful cleavage. As seen
in Figure S6, all incompletely exfoliated bulks show stepwise
edges with peeled nanosheets within 500 nm adhered on their
surfaces, confirming the successful exfoliation of (TPrA)-
Cu2(dca)5. As SEM only can offer information about the lateral
lengths of flakes, we further perform AFM to check the thickness
of the terraces. As seen in Figure S7, the incompletely exfoliated
bulks with different color contracts show terraces at their edges.
The height profile displays several steps which are approximately
5−10 nm in thickness (Figure S7). To observe the exfoliated
nanosheets more directly, we dilute the aforementioned
suspension to 0.02 mg/mL to minimize agglomeration, and
then the suspensions were dipped on preheated Si wafers which
were left to stand until the complete evaporation of the solvent.
As shown in Figure 5a,b, the exfoliated nanosheets with a lateral
size of about 341 nm agree with the SEM result, and the heights
of steps measured in the height profile are 8.9, 13.6, 4.1, 13, 31.8,
59.3 and 12.3 nm, respectively.
In addition, we performed TEM to investigate the crystalline
and check the cleavage direction of the sonication exfoliated
nanosheets. As illustrated in Figure 5c, the bright-field image
shows the flat (TPrA)Cu2(dca)5 nanosheets with various
dimensions stacked like overlapped leaves. The lateral distance
of the nanosheets ranges from 200 to 500 nm. The stepwise
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morphology of these nanosheets indicates incomplete peeling,
which could arise from the restacking of the exfoliated
nanoflakes possibly through the strong electrostatic attractions.
The HRTEM image was collected at the edge of the exfoliated
nanosheets and is displayed in Figure 5d. The lattice fringe
shows an interplanar distance of about 0.52 nm, which can be
associated with the (221) plane as it agrees well with its d-
spacing of 0.52 nm. More importantly, the SAED patterns were
collected normally to the nanosheets to verify their atomic-level
ordered structure. The diffracted spots in Figure 5d inset
correspond to the (221) and (2−21) planes of the (TPrA)-
Cu2(dca)5 nanosheets. This result associated with the HRTEM
image indicates that the (TPrA)Cu2(dca)5 was exfoliated
parallel to the (−102) plane and the (−102) is the slippery
facet, which verified our aforementioned conjecture and agrees
well with our nanoindentation and high-pressure synchrotron X-
ray diffraction results.
■ CONCLUSIONS
In summary, the mechanical properties of a new hybrid
framework (TPrA)Cu2(dca)5 have been systematically inves-
tigated by experimental approaches and first-principles calcu-
lations. Nanoindentation tests show that Young’s modulus of
(−102) is 65% larger than that of the (002) plane, indicating a
1.65 bonding strength anisotropy between the two faces.
Furthermore, the discrete plastic deformations on the loading
part of the (020) plane demonstrate that the 2D [Cu2(dca)4]
planes have the least attachment energy and the 3D framework is
prone to cleavage along the <−102> direction, namely, piled
parallel to (−102) plane, to make displacement bursts in the P−
h curves. Inhomogeneous pile-ups around the indenter
impressions also verified this result. We have also probed the
hydrostatic properties of the (TPrA)Cu2(dca)5 via high-
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Crystal Growth & Design
pressure synchrotron X-ray powder diffraction experiments,
which were performed from ambient to 3.36 GPa. This study has
demonstrated that the d-spacing of (−102), (100), and (020)
shrank 9.7, 7.1, and 9.1% during the compression process,
showing the more rigid nature of the 2D [Cu2(dca)4] layer.
Although (TPrA)Cu2(dca)5 adopts a nonporous structure, its
bulk modulus calculated via the second-order Birch−Murna-
ghan equation is 6.97 GPa lying in the range of values for porous
MOFs, indicating its much softer nature under hydrostatic state.
Furthermore, the full elastic constants of the framework
(TPrA)Cu2(dca)5 were calculated by first-principles calcula-
tions, and the result indicated that the anisotropy of Young’s
moduli and shear moduli are an order of magnitude larger than
both common porous and dense frameworks, even higher than
many typical 2D structures, indicating that this material is more
similar to 2D materials compared with 3D materials in response
to uniaxial and shearing stresses. This feature demonstrates that
the 3D framework (TPrA)Cu2(dca)5 could produce structure
slippery and consequently be exfoliated into nanosheets like 2D
structures under compression or stretching. The values of
Poisson’s ratio reflect that the boundary nature of (TPrA)-
Cu2(dca)5 is between brittle and ductile. Furthermore, SEM,
AFM, and TEM characterization gave direct evidence of the
successful exfoliation of (TPrA)Cu2(dca)5, and the HR-TEM
image and SAED manifest that this 3D structure can be peeled
along to (−102) plane, which agree well with the nano-
indentation results. Considering the soaring demand for
searching for new 2D materials, this study could be instructive
for selecting 3D structures which have extreme mechanical
anisotropy and can be exfoliated into 2D nanosheets.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.cgd.2c00658.
Summary of the elastic properties of (TPrA)Cu2(dca)5
and other prototypical 2D structures, material’s informa-
tion of (TPrA)Cu2(dca)5 including crystallographic
information, selected bond lengths and angles, and
asymmetric unit, and characterizations including powder
X-ray diffraction, nanoindentation, high-pressure syn-
chrotron powder diffraction, SEM, and AFM of the newly
synthesized (TPrA)Cu2(dca)5 (PDF)
Accession Codes
CCDC 2083249 contains the supplementary 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
Wei Li − School of Materials Science and Engineering & Tianjin
Key Laboratory of Metal and Molecule-Based Material
Chemistry, Nankai University, Tianjin 300350, China;
orcid.org/0000-0002-5277-6850; Email: wl276@
nankai.edu.cn
Guo-Qiang Feng − Department of Physics and Mechanical &
Electrical Engineering, Hubei University of Education, Wuhan
430074, China; Email: gqfeng627@outlook.com
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pubs.acs.org/crystal Article
Authors
Li-Jun Ji − Department of Physics and Mechanical & Electrical
Engineering, Hubei University of Education, Wuhan 430074,
China; School of Materials Science and Engineering & Tianjin
Key Laboratory of Metal and Molecule-Based Material
Chemistry, Nankai University, Tianjin 300350, China;
orcid.org/0000-0001-9006-788X
Zhi-Gang Li − School of Materials Science and Engineering &
Tianjin Key Laboratory of Metal and Molecule-Based Material
Chemistry, Nankai University, Tianjin 300350, China
Li-Yuan Dong − School of Science, Jiangsu University of Science
and Technology, Zhenjiang 212100, China
Ying Zhang − School of Materials Science and Engineering &
Tianjin Key Laboratory of Metal and Molecule-Based Material
Chemistry, Nankai University, Tianjin 300350, China
Tian-Meng Guo − School of Materials Science and Engineering
& Tianjin Key Laboratory of Metal and Molecule-Based
Material Chemistry, Nankai University, Tianjin 300350,
China
Fei-Fei Gao − School of Materials Science and Engineering &
Tianjin Key Laboratory of Metal and Molecule-Based Material
Chemistry, Nankai University, Tianjin 300350, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.cgd.2c00658
Funding
We acknowledge the financial support from the Guiding Project
of Education Scientific Research Plane in the Hubei Provincial
Department (No. 82021257) and the National Natural Science
Foundation of China Youth Science (No. 22205059).
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
Calculation support from the Institute of Theoretical Physics of
the Hubei University of Education is gratefully acknowledged.
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