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Bistable Optoelectronic Properties Originated from the Scissoring

Motion of the TEMPO Skeleton in Supramolecular Radical
Ferroelectrics
Yongfa Xie,* Teng-Fei Li, Wei Chen, Lixin Liang, Hui-Peng Lv, Qing Liu, Yin-Shan Meng,
Guangjin Hou,* and Hu Cai*
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ABSTRACT: Bistable materials with multiphysical channels, such

as optical, electrical, and magnetic properties, have been paid
dramatic attention due to their alternativity of the signal status in
electronic devices. Herein, three stable supramolecular radicals
([(NH3-TEMPO)(18-crown-6)][XF6] (1, X = P; 2, X = As; 3, X =
Sb)) were synthesized and characterized. The former two
molecules present ferroelectric phase transitions around 381.7
and 382.7 K, respectively, with bistability in dielectric property and
second-harmonic generation (SHG) effect, which are first found in
supramolecular radicals. Their ferroelectric transition and bistable
properties are generated from a net polar crystal structure owing to
the static ordered packing of NH3-TEMPO radical cations in the
low-temperature phase (LTP) to a nonpolar structure owing to a distinctive symmetric scissoring motion of NH3-TEMPO radical
cations between two 18-crown-6 molecules in the high-temperature phase (HTP). Both of them exhibit paramagnetic properties in
HTP and LTP states since no intermolecular spin−spin interaction occurs due to the long distances among the radicals in their
crystals. These results make us possible to design bistable optoelectronic radical materials with bistability in magnetic property in the
future.

■ INTRODUCTION
Bistable materials possessing two different states of physical
electric [(NH3-TEMPO)(18-crown-6)][ReO4], whose ferroe-
lectricity can be maintained above room temperature.31
channels, such as optical, electrical, magnetic, and mechanical Nevertheless, the reported ferroelectrics with the TEMPO
properties, have attracted extensive concentration due to their radical did not show bistability in dielectrics and second-
great potential to realize seamless integration of multifunc- harmonic generation (SHG) effect although many other
tional properties in one single device.1−4 Among them, nonradical supramolecules exhibit these bistable properties.32
dielectric and nonlinear optical properties with bistable This limits their application in electronic devices due to the
characteristics often exist in many functional materials, such lack of signal switching in different states. According to the
as ferroelectrics, ferroelastics, ferromagnets, etc.5−10 The reported supramolecular ferroelectrics,33,34 the rotation of
bistability in many physical channels greatly improves the crown ether molecule, the pendulum-like motion of cation, and
flexibility to control and retrieve the alternativity of the signal the rolling of anion could cause ordered to disordered
status. Some organic radicals with bistabilities in multiphysical structure upon increasing the temperature and result in
channels, such as magnetism, conductivity, color, and IR bistabilities in optoelectronic properties. Herein, the tetrahe-
transmittance due to the structural phase transition, were dral anions in [(NH3-TEMPO)(18-crown-6)][ReO4]/[ClO4]
reported.1,11−21 Nitroxyl radicals were usually designed as were replaced by octahedral anions PF6−/AsF6−/SbF6−; as a
bistable magnetic materials arising from a radical/dimer result, three novel supramolecules ([(NH3-TEMPO)(18-
interconversion (Figure 1a).22−28 However, nitroxyl radicals
with other bistable optoelectronic physical properties besides
magnetism are rarely found as bistable multifunctional Received: January 5, 2023
materials. Owing to the relatively high stability of nitroxyl
radicals,8,29,30 it is well worth excavating their bistability in
other physical channels besides magnetic channels.
In 2021, we had first anchored a 4-amino-TEMPO radical
into 18-crown-6 and formed a supramolecular radical ferro-

© XXXX American Chemical Society https://doi.org/10.1021/acs.inorgchem.3c00041

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[(NH3-TEMPO)(18-Crown-6)][AsF6]. Equimolar NH2-TEMPO and

18-crown-6 were dissolved in methanol, and an equivalent of LiAsF6
in methanol was added to the solution. Then, stoichiometric amounts
of formic acid were dropped into the clear solution to make it acidic.
After several days, the red block crystals of compound 2 were
obtained by filtration. 1H NMR (300 MHz, CD3OD) δ 3.73 (s, 24
H); 13C{1H} NMR (75 MHz, CD3OD) δ 69.77 (s); 19F{1H} NMR
(282 MHz, CD3OD) δ −62.27, −65.49, −68.89, −72.08 (q). 1H
NMR and 13C{1H} NMR signals of the TEMPO skeleton could not
be observed owing to the paramagnetic nature of the nitroxide spin
labels. Elemental analysis, Found: C, 40.37; H, 7.02; N, 4.40%; calcd
for C21H44AsF6N2O7•: C, 40.32; H, 7.09; N, 4.48%.
[(NH3-TEMPO)(18-Crown-6)][SbF6]. Equimolar NH2-TEMPO and
18-crown-6 were dissolved in methanol, and an equivalent of NaSbF6
in methanol was added to the solution. Then, stoichiometric amounts
of formic acid were dropped into the clear solution to make it acidic.
After several days, the red block crystals of compound 3 were
obtained by filtration.
NMR Spectra Measurements. The solution NMR spectra were
Figure 1. (a) Nitroxyl radicals with magnetic bistability. (b) recorded on Bruker Advanced NEO 300 MHz Digital NMR
Supramolecular radicals with bistable optoelectronic properties spectrometers. Chemical shifts of 1H NMR and 13C NMR are
originated by the scissoring motion of NH3-TEMPO radical cations. reported in parts per million (ppm) downfield from tetramethylsilane
(TMS) at δ = 0.00 ppm. Chemical shifts of 19F NMR and 31P NMR
are reported in parts per million (ppm) downfield from CFCl3 and
crown-6)][PF6](1), [(NH3-TEMPO)(18-crown-6)][AsF6]- H3PO4 at δ = 0.00 ppm, respectively. Coupling constants (J) are
(2), and [(NH3-TEMPO)(18-crown-6)][SbF6](3)) were reported in Hz and referred to apparent peak multiplications.
obtained (Figure 1b). Interestingly, the former two radical The solid-state NMR experiments were carried out using a wide-
compounds experienced a disordered/ordered structural phase bore 14.10 T AVIII 600 with a 4 mm WVT HX MAS NMR probe
under 8 kHz MAS rate. The 31P single-pulse experiments were
transition due to the scissoring motion of the TEMPO
acquired using 90° pulse for excitation, and the corresponding radio
skeleton (Figure 1b). The motion is another unique mode frequency (RF) amplitude and pulse duration were 34 kHz and 7.3 μs,
different from the pendulum-like motion33,35 and rotation respectively. During signal acquisition, SPINAL64 decoupling
motion36 of ammonium cations in the reported crown ether sequence was applied on the 19F channel, with an RF amplitude of
clathrates (Figure S1). Termination of the scissoring motion of 30 kHz. The recycle delay for the one-dimensional (1D) 31P NMR
the TEMPO skeleton in these two compounds results in the experiments was 2.0 s, and the temperature was escalated from 293 to
polar crystal structure at the low-temperature phase (LTP) 393 K with 10 K increment. The full width at half-maximum
state. Thus, ferroelectricity was observed in their dropped film (FWHM) values of 31P signals were extracted via deconvolution of
devices. Most importantly, these two supramolecular radicals 1D 31P NMR spectra using a single peak of pure Lorentzian line
display bistability in dielectric and SHG properties due to the shape.
Single-Crystal X-Ray Diffraction Measurements. Single-
alternative change between the scissoring motion of the crystal X-ray diffraction data of 1 and 2 were measured on a Rigaku
TEMPO skeleton in the high-temperature phase (HTP) state Saturn 924 diffractometer with Mo Kα radiation (λ = 0.71073 Å).
and its termination motion in the LTP state. Both exhibit Data collection, cell refinement, and data reduction were performed
paramagnetic properties in the HTP and LTP states because of using Rigaku Crystal Clear 1.3.5. The structures were solved by direct
the single electron behavior without interaction. In short, methods and refined by the full-matrix least-squares method based on
bistable optoelectronic physical channels besides paramagnet- F2 with the SHELXTL software package. All nonhydrogen atoms were
ism were revealed in stable supramolecular nitroxyl radicals refined anisotropically and the positions of all hydrogen atoms were
originating from a unique vibration mode of scissoring motion generated geometrically. The data collection and structure refinement
of TEMPO skeleton. These results are of extraordinary help in of these crystals are summarized in Table S1. The X-ray crystallo-
graphic structures have been deposited at the Cambridge Crystallo-
the future design of bistable optoelectronic organic radical graphic Data Centre (deposition numbers CCDC: 2145358−
materials with bistability in magnetic property. 2145362, 2236142−2236143) and can be obtained free of charge

■ EXPERIMENTAL SECTION
Synthesis. All of the chemical reagents in the synthesis were of
from the CCDC via www.ccdc.cam.ac.uk/getstructures.
Powder X-Ray Diffraction (PXRD). Variable-temperature (VT)
PXRD data were measured on a Rigaku D/MAX 2000 PC X-ray
reagent grade and used without further purification. diffractometer with Cu Kα radiation. Diffraction patterns were
[(NH3-TEMPO)(18-Crown-6)][PF6]. Equimolar NH2-TEMPO and collected in the 2θ range of 5−50° with a step size of 0.02°. The
18-crown-6 were dissolved in ethanol/acetonitrile (vol/vol = 3/1), 2θ scanning speed was set as 2.0° min−1. The HTP structure of
and then an equivalent of HPF6 (60% in water) was added dropwise. compounds 1 and 2 was obtained by Rietveld refinements against
The mixed solvent was added to the mixture till the mixture became a PXRD data measured at 413 K using TOPAS Academic (TA).38−40
clear solution. After several days, the red block crystals of compound 1 The NH3-TEMPO and 18-crown-6 were set as rigid bodies during the
were obtained by filtration. 1H NMR (300 MHz, CD3OD) δ 3.74 (s, structure solution and refinements. Thus, there are only 6 degrees of
24 H); 13C{1H}(for proton-decoupled) NMR (75 MHz, CD3OD) δ freedom for translation and rotation in each molecule when solving
69.74 (s); 19F{1H} NMR (282 MHz, CD3OD) δ −72.95, −75.46 (d, the crystal structures of compounds 1 and 2 although they contain
1
JFP = −706); 31P{1H} NMR (121 MHz, CD3OD) −126.86, −132.69, large cell sizes and numbers of atoms in the unit cell.
−138.52, −144.35, −150.17, −155.99, −161.81, (heptet, 1JPF = SHG and Dielectric Measurements. To complete second-
−705). 1H NMR and 13C{1H} NMR signals of the TEMPO skeleton harmonic generation (SHG) experiments, an unexpanded laser beam
could not be observed owing to the paramagnetic nature of the with low divergence (pulsed Nd:YAG at a wavelength of 1064 nm, 5
nitroxide spin labels.37 Elemental analysis, Found: C, 43.17; H, 7.41; ns pulse duration, 1.6 MW peak power, 10 Hz repetition rate) was
N, 4.70%. calcd for C21H44F6N2O7P•: C, 43.37; H, 7.63; N, 4.82%. used. The instrument model is Ins 1210058, INSTEC Instruments,

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while the laser is Vibrant 355 II, OPOTEK. Complex dielectric

permittivity was measured with a TH2828A impedance analyzer.
Silver conductive paste deposited on the plate surfaces of samples was
used as top and bottom electrodes.
Ultraviolet−Visible (UV−Vis) Absorbance Spectra. Ultra-
violet−visible (UV−vis) absorbance spectra of 1 and 2 were measured
on powder samples with BaSO4 as a matrix by using a Shimadzu
(Tokyo, Japan) UV-2600 spectrophotometer at room temperature.
Electron Paramagnetic Resonance (EPR) Measurements.
The continuous-wave (CW) electron paramagnetic resonance (EPR)
spectra were recorded on a Bruker Elexsys E500 spectrometer with a
superhigh sensitivity probe (ω = 9.36 GHz) using a 4 mm EPR
sample tube.
Magnetic Property Measurements. Magnetic susceptibility
data were collected using a Quantum Design MPMS XL-5 or
Figure 2. DSC chart of compounds 1 (red line) and 2 (blue line)
PPMS-9T (EC-II) SQUID magnetometer. Measurements for all of
the samples were performed on microcrystalline powder restrained by with a heating/cooling rate of 20 K min−1. The upper lines are heating
a parafilm and loaded in a capsule. The magnetic susceptibility data runs, and the lower lines are cooling runs. The spectral anomalies at
were corrected for the diamagnetism of the samples using Pascal 364 and 385 K are the artifacts dependent on the measurement
constants and a sample holder and parafilm by corrected measure- system.
ment.
Thermal Analyses. Differential scanning calorimetry (DSC)
measurements were recorded on a NETZSCH DSC 200F3
instrument by heating and cooling crystalline samples with a rate of
20 K min−1 in aluminum crucibles under a nitrogen atmosphere.
Thermogravimetric analyses (TGAs) were carried out on a
PerkinElmer TGA 8000 instrument by heating crystalline samples
with a rate of 40 K min−1 under a nitrogen atmosphere.
Elemental Analysis. Elemental analysis was carried out on an
Elemantar Vario EL cube with CHN mode. The mean content values
of C, H, and N were calculated from twice the measurements of each
compound.

■ RESULTS AND DISCUSSION

Thermal Analyses. Compounds 1, 2, and 3 were obtained
by the slow evaporation of the solution of the corresponding
mixture in ethanol or methanol. Their chemical purity, phase
purity, and chemical composition were confirmed by elemental
analysis, powder X-ray diffraction (PXRD) analysis, single-
crystal XRD, and nuclear magnetic resonance (NMR) spectra ( Figure 3. Asymmetric units of 1 at room temperature (a) and at 413
Supporting Information). Differential scanning calorimetry K (modeled by the PXRD data) (b). The packing structures of 1 from
the b-axis direction at room temperature (c) and from the a-axis
(DSC) measurement is a common method to detect whether a direction at 413 K (modeled by the PXRD data) (d). Green arrows
compound undergoes a structural phase transition under indicate the dipole moment direction of NH3-TEMPO radical cations.
external temperature stimulation. A free radical compound The hydrogen atoms were omitted for clarity.
[(NH3-TEMPO)(18-crown-6)][PF6] (1) shows a pair of
reversible thermal anomaly peaks during the heating/cooling
process, pointing out reversible phase transition (Tc) above energy in comparison to the tetrahedral ReO4 and ClO4
room temperature of 381.7/371.3 K (Figure 2). Near the anions in the reported supramolecular radicals.
phase transition temperature, compound 1 experiences a The average enthalpy changes (ΔH) of compound 1 during
packing structural change between Pna21 and a higher the phase transition are 1.45 kJ·mol−1 and the average entropy
symmetric structure Cmcm as mentioned below (Figure 3). change (ΔS) can be calculated by the formula ΔS = ΔH/T to
Free radical compound [(NH3-TEMPO)(18-crown-6)][AsF6] be 3.84 J·mol−1·K−1. Then, according to the Boltzmann
(2) shows an irreversible thermal anomaly peak at 296.7 K equation ΔS = R·ln N (where R is the general gas constant, N
(Tc1) in the heating run and a couple of reversible thermal is the ratio of the order in HTP to LTP), N values of 1.6 were
anomaly peaks at 382.7/377.0 K (Tc2) during the heating/ obtained. Correspondingly, ΔH, ΔS, and N for the irreversible
cooling process (Figure 2). In the heating run, compound 2 phase transition of compound 2 are 0.69 kJ·mol−1, 2.31 J·
undergoes a packing structural change from Pna21 to Cc mol−1·K−1, and 1.3, respectively, and ΔH, ΔS, and N for the
around 296.7 K and another structural phase change from Cc reversible phase transition of compound 2 are 0.33 kJ·mol−1,
to a higher symmetric structure Cmcm. In the cooling run, it 0.88 J·mol−1·K−1, and 1.1, respectively.
experiences a structural change from Cmcm directly to Pna21. Crystal Structure of [(NH3-TEMPO)(18-crown-6)][PF6].
Their phase transition temperatures are higher than most of Compound 1 crystallizes in a polar space group of Pna21 in an
the 18-crown-6-based ferroelectrics,32 and they reveal high orthogonal crystal system with cell parameters of a =
thermal stability as shown in the TGA graph (Figure S2). 15.8565(8) Å, b = 10.9886(7) Å, c = 16.4827(8) Å, and V =
Thermal hysteresis can be observed in these two compounds 2872.0(3) Å3 at room temperature (Table S1). Its asymmetric
probably because the introduction of octahedral PF6 and AsF6 unit contains one [NH3-TEMPO] radical cation, one 18-
anions may decrease the order/disorder phase transition crown-6 molecule, and one PF6− anion (Figure 3a). The
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ammonium group of [NH3-TEMPO] radical cations has an indicating that the HTP shows a higher symmetry than the
interaction with 18-crown-6 molecule through N−H···O LTP in the crystal structure. The 413 K diffraction pattern in
hydrogen bonds (Table S2). The [NH3-TEMPO] radical the heating process can be indexed (Figure S5) by an
cation and PF6− anion have an orientated disordered structure orthorhombic space group of Cmcm (a = 11.1333(7) Å, b =
at room temperature with two orientations of occupancies 0.60 15.9124(12) Å, c = 17.0057(11) Å, V = 3012.7(4) Å3) in the
and 0.40 (Figure 3a), while the fully ordered structure with the centrosymmetric point group of D2h (Table S1), and a highly
same space group was observed in the crystal structure at 173 disordered structure was then solved, which are shown in
K (Figure S3). From the packing view of the crystal structure Figure 3b,d. The crystal structure motifs are given in the
along the b-axis, the NH3-TEMPO···18-crown-6 supramolec- standard axis, and the relationship between the two structural
ular cations pack along the c-axis approximately, which forms cells of HTP and LTP is a413K ≈ b298K, b413K ≈ −a298K, and
polarization along the c-axis in the C2v packing structure c413K ≈ c298K (Figure 3c,d). In the HTP, the 18-crown-6
(Figure 3c). Regrettably, in the HTP, the single-crystal molecules perform rotation motion around 4 orientations,
diffractions are seriously diffused and could not be solved. which could not lead to the reorientation of the molecular
Thus, the variable-temperature PXRD measurements of the dipole moment since it is along the rotation axis (Figure 3b,d).
sample were carried out. By increasing the temperature, it can The PF6− anions with an approximate Oh symmetry act as
be observed that the PXRD patterns below phase transition rolling motion mode, which could not introduce an obvious
temperature Tc (383, 373, 363, 353, 333, 313 K) are consistent net molecular dipole moment, either. Furthermore, the NH3-
with those at 298 K (Figure 4). This agrees with the fact that TEMPO radical cations achieve vibration with two orienta-
tions and a unique movement pattern of scissoring motion
between two neighbored 18-crown-6 molecules. This move-
ment pattern is distinctive from the pendulum-like motion of
4-methoxyanilinium, which results in ferroelectric phase
transition in crown ether clathrates reported by Xiong et
al.,33,35 and the rotation motion of m-fluoroanilinium, which
exhibits dipole rotation by electronic stimulation and leads to a
ferroelectric transition in crown ether clathrates reported by
Nakamura36 (Figure S1). The scissoring motion of the NH3-
TEMPO radical cations makes the crystal a symmetric
structure and results in dipoles along the c-axis canceling
each other at the HTP while slowing down the scissoring
motion of the NH3-TEMPO radical cations at room
temperature, leading to dipoles along the c-axis.
To investigate the rotation mode of the 18-crown-6
Figure 4. Variable-temperature PXRD measurements of compound 1 molecules, an attempt was made to perform the variable-
below and above the phase transition temperature. The intensities for temperature (VT) solid-state 1H NMR and 13C NMR
each temperature were normalized. measurements of compound 1, but this was not successful
due to the paramagnetic nature of the nitroxyl radical. Since
the crystal phase does not change below Tc, and there is a the 19F NMR background signal of the probe is greatly
slight increase in the crystal cell volumes (Figure S4) due to dependent on the temperature, the obtained solid-state 19F
the thermal expansion. However, some of the reflections in NMR data are difficult to analyze. Thus, only the VT solid-
PXRD disappear as the temperature increases above Tc (413, state 31P magic angle spinning (MAS) NMR spectra were
403, 393 K), especially in the marked region (Figure 4), obtained successfully. All of the 31P NMR spectra contain

Figure 5. (a) 1D VT single-pulse 31P MAS NMR spectra from 293 to 393 K, with 19F decoupling and at 8 kHz MAS rate; (b) 31P chemical shifts
(ppm) as a function of temperature (K). The linear fitting was presented in the red line, using δ(31P) = a × T (K) + b, where a = −0.087 ± 0.002
ppm K−1, b = −104.3 ± 0.5 ppm, and R2 = 0.9963. (c) Plot of FWHM (kHz) of 31P NMR signals as a function of temperature (K).

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Figure 6. Dielectric measurements of compounds 1 (a) and 2 (b) on pressed-powder pellets. The dielectric bistable states switch between the LTP
and HTP in compounds 1 (c) and 2 (d).

single resonance with isotropic chemical shifts and line width, compound 2 are similar to those of compound 1 (Figure S7),
both of which vary with temperature increased from 293 to only does the angle of β tilt to 91.412(7)° in its crystal cell
393 K, as shown in Figure 5a. The linear response of 31P NMR (Table S1). The fully ordered structure is observed at room
chemical shift to temperature, as shown in Figure 5b, may be temperature and a net dipole parallel to a- and c-plane is
attributed to the thermal effect.41 On the other hand, the line formed due to the ordered arrangement of NH3-TEMPO
shapes of 31P NMR signals were pure Lorentzian; in other radical cations (Figure S7c). Its crystal structure in the HTP
words, the transverse relaxation of 31P time-domain FID signals could not be solved due to the seriously diffused diffraction
was purely exponential, I (t) = I0* exp(−t/T_2) (I0 represents spots, either. So variable-temperature PXRD analysis was also
the signal intensity and T2 represents transverse relaxation studied for compound 2. Above Tc2 (413, 403, 393 K), some of
constant). As the temperature increases to 360 K, the full the reflections in the PXRD disappeared in comparison to that
width at half-maximum (FWHM) of the 31P NMR signals of the LTP (below Tc2) (383, 373, 363, 353, 333, 313, 298 K),
slightly decreases (Figure 5c), which indicates the acceleration especially in the marked region (Figure S8). This illustrates
of the rolling rate of the PF6 anions in the LTP. However, that compound 2 possesses a higher symmetric crystal
FWHM drops sharply at around 380 K, suggesting that the structure in the HTP than that in the LTP. In the LTP, the
pure Lorentzian line shape was altered by the fluctuating field crystal phase does not change below Tc2 and there is a slight
from the electric dipolar moment of radicals due to the phase increase in the crystal cell volumes with a β angle decreasing
transition, according to the previous report. 42 As a closely to 90° (Figure S9) due to the thermal expansion.
consequence, the rolling rate of PF6− anions in the HTP is Refinement of the 413 K diffraction pattern (Figure S10) in
much higher than that in the LTP. This result is also consistent the heating process gave a highly disordered structure in the
with the disordered and ordered crystal structures in the HTP orthogonal crystal system packing with a space group of Cmcm
and LTP, respectively. (a = 11.1829(5) Å, b = 16.0060(8) Å, c = 17.0516(8) Å, V =
Crystal Structure of [(NH3-TEMPO)(18-crown-6)]- 3052.1(2) Å3) in the centrosymmetric point group of D2h
[AsF6]. Compound 2 crystallizes in a polar space group of (Table S1). In the HTP, similar to compound 1, the 18-crown-
Pna21 in the orthogonal crystal system with fully ordered 6 molecules perform rotation motion, and the AsF6− anions
structure and cell parameters of a = 15.7774(4) Å, b = perform rolling motion mode. Both of them could not produce
10.9749(4) Å, c = 16.4433(5) Å, and V = 2847.25(15) Å3 at a a net molecular dipole moment (Figure S7c,d). In this case, the
low temperature (173 K) (Figure S6 and Table S1). As NH3-TEMPO radical cations also achieve vibration with two
temperature increases, it experiences an irreversible phase orientations and a distinctive motion of scissoring motion
transition at 296.7 K, and then it crystallizes in a polar space between two neighbored 18-crown-6 molecules (Figure S7d).
group of Cc in a monoclinic crystal system with cell parameters This scissoring motion makes the crystal a symmetric structure
of a = 10.9403(8) Å, b = 15.7661(9) Å, c = 16.9504(10) Å, β = and results in dipoles canceling each other in the crystal at the
91.412(7)°, and V = 2922.8(3) Å3 at room temperature. With HTP (Figure S7d) while termination of the scissoring motion
replacing the PF6− anion with AsF6−, the components in the of the NH3-TEMPO radical cations at room temperature leads
asymmetric unit and packing form in the crystal structure of to dipoles parallel to the a- and c-plane (Figure S7c).
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Figure 7. Temperature-dependent SHG measurement of compound 1 (a) with single crystals (size: 0.5−1.0 mm, the direction of laser is parallel to
the c-axis of single crystals). SHG behavior of compound 2 (b) with a block single crystal (0.20 × 0.15 × 0.12 mm3) was measured in the plane of
a- and b-axis in the direction, which could obtain the highest SHG intensity. The SHG bistable states switch between the LTP and HTP in
compounds 1 (c) and 2 (d).

Crystal Structure of [(NH3-TEMPO)(18-crown-6)]- theoretical saturated polarization values (Table S3). Further-
[SbF6]. Compound 3 crystallizes in a polar space group of more, recoverable dielectric switching was found during several
Cc in a monoclinic crystal system as compound 2, with cell running cycles between the LTP and HTP, illustrating the
parameters of a = 11.0075(6) Å, b = 15.8388(9) Å, c = bistable dielectric behavior in these two radicals (Figure 6c,d).
17.0415(10) Å, b = 91.350(5) Å, and V = 2970.3(3) Å3 at The dielectric behavior means their electric polarization
room temperature. Its polar space group was also verified by an behaviors arise reversible bistability between the LTP and
obvious SHG signal observed at room temperature (Figure HTP. Speculatively, the alternative electric polarization
S11). This crystal has the same packing structure as compound behaviors by temperature stimulation mainly originated from
2 just alternating the anions instead of SbF6− (Figure S12 and the scissoring motion of NH3-TEMPO radical cations at the
Table S1). Unfortunately, pure crystals of compound 3 could HTP and their termination motion at the LTP. To our
not be obtained, as indicated by the PXRD patterns in knowledge, the reversible bistability behavior of electric
comparison to the simulated one (Figure S14) even though polarization is first found in supramolecular radicals.
crystallization was carried out several times. In that case, it SHG Effect. According to the crystal structure mentioned
obstacles us to further study the optoelectronic properties of above, the crystal space group (C2v) of compound 1 at 298 K
compound 3. belongs to a non-centrosymmetric point group, which should
Dielectric Properties. To further determine the macro- have an SHG effect except 622, 432, and 422 point groups in
scopic physical quantity deriving from the electric polarization visible and near-IR regions according to Kleinman symmetry.43
microscopic process, the temperature-dependent real part (ε′) The direction of the laser is parallel to the c-axis of the single
curve of the complex dielectric permittivity of these two crystals when measuring the SHG signal. As we expected, its
compounds was carried out by applying an external electric crystals exhibit an SHG signal around 0.16−0.09 V (SHG on
field E. The real part (ε′) of the dielectric constant of both state) at the LTP state (below Tc), and their SHG response
compounds 1 and 2 exhibits step-like change during the drops dramatically in the vicinity of Tc as the temperature
heating and cooling process (Figure 6a,b). The temperatures of increases, while a zero SHG signal (SHG off state) was
significant dielectric anomalies appear around 382 and 383 K detected at the HTP state during the heating process. In the
for compounds 1 and 2 in the heating run, respectively, which cooling process, it also shows the SHG off and on states,
are consistent with their phase transition temperatures indicating a reversible SHG response (Figure 7a). This
measured by DSC. And they reveal the value of dielectric phenomenon also can be explained that compound 1
constant around 2 at the LTP and around 6 at the HTP in the experiences structural phase transition between a polar point
heating and cooling runs. Similar dielectric constants were group of mm2 and an indexed nonpolar point group of mmm
found for compound 2 at the LTP in the heating process and due to the static packing of NH3-TEMPO radical cations in the
the cooling process, although it has different crystal structures LTP and their scissoring motion in the HTP, respectively. In
in the two processes (Cc/Pna21 in the heating/cooling runs), addition, the SHG on/off states of compound 1 could be
probably because these two crystal structures display similar switched several running cycles between the LTP and HTP,
F https://doi.org/10.1021/acs.inorgchem.3c00041
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry pubs.acs.org/IC Article

Figure 8. CW-EPR measurement of a polycrystalline sample of compounds 1 (red line) and 2 (blue line) at room temperature with a sweeping
magnetic field range of 500 G and a microwave power of 0.7963 mW (a). UV−visible absorption of compounds 1 (red line) and 2 (blue line) in
the solid state (b).

Figure 9. χMT (blue dotted line) and χM (red dotted line) versus T plots for (a) 1 and (b) 2 under 1 kOe applied magnetic field.

and the SHG signal intensities in LTP keep around 0.90 V signals without hyperfine splitting were observed for radical
after several running cycles (Figure 7c), which greatly compounds 1 and 2 with g values of 2.0059 and 2.0074,
maintains the bistable SHG states in this novel supramolecular respectively. The broad EPR peak of these supramolecular
radical material. Compound 2 crystallizes in a space group of radicals is due to their strong spin−spin (dipole−dipole)
Cc at 298 K, which also belongs to a polar point group of Cs, interaction in the solid state.28,44 This is powerful evidence to
and a net dipole moment parallel to the a- and c-plane is confirm the existence of a single radical. Besides, the solid-state
originated by the packing of static NH3-TEMPO radical UV−vis absorption spectra further verify the nitroxyl radicals.
cations. Thus, its crystals also exhibit SHG signal with a value As shown in Figure 8b, there is an absorption peak at 460 nm,
around 0.35 V at the LTP state, which is stronger than that of indicating the nitroxyl radical (−NO•) group.45 Both of these
compound 1. Zero SHG signal was also observed at the HTP measurements demonstrate nitroxyl radicals in the crystals.
state due to the canceled dipole moment generated by the Furthermore, the variable-temperature magnetic susceptibil-
scissoring motion of NH3-TEMPO radical cations, and it ities for 1 and 2 were performed under a DC field of 1.0 kOe
shows reversible SHG on/off states during the heating and from 2.0 to 390 K. As shown in Figure 9, the χMT−T plots are
nearly horizontal lines. The room-temperature χMT values of
cooling processes (Figure 7b). Its SHG on/off states also could
0.385 and 0.375 cm3·K·mol−1 for 1 and 2, respectively, are
be switched several running cycles, indicating the bistable SHG
consistent with the theoretical value for a free radical, which
behavior (Figure 7d). The bistable SHG behavior for
indicates the existence of an unpaired electron. As the
compound 2 interprets that its structural phase transitions go
temperature increased to 390 K, the χMT values of 1 and 2
through from m to mmm in the heating process and mmm to remain unchanged, and there is no thermal hysteresis
mm2 in the cooling process. It shows similar SHG values at the phenomenon in the vicinity of the phase transition temper-
LTP in the heating and cooling process also probably due to ature. Meanwhile, the relationship between χM and T (2−390
the similar theoretical polarization values of the two crystal K) follows the Curie−Weiss law. Most of the spin density is
structures (Cc and Pna21) (Table S3). It is worth mentioning localized around the nitrogen and oxygen atoms of the
that the bistability phenomenon in SHG behavior does not aminoxyl group in the TEMPO skeleton and the amount of
display in the reported analog supramolecular radicals [(NH3- spin density on these two atoms is nearly equal.46 Therefore,
TEMPO)(18-crown-6)][ReO4] and [(NH3-TEMPO)(18- the intermolecular distances between the midpoints of N−O
crown-6)][ClO4]. bonds in the nearest neighbored NH3-TEMPO molecules were
EPR, UV−Visible, and Magnetic Properties. Both checked. They are 9.01 and 7.47 Å in the crystal for compound
compounds 1 and 2 contain TEMPO radicals in the crystal 1 at room temperature and 413 K, and 9.60 and 8.02 Å in the
structure. To confirm their spin state, the powder of their crystal for compound 2 at room temperature and 413 K,
crystals was tested with CW-EPR at room temperature. In respectively (Figures S16 and S17). That long distances cannot
Figure 8a, broad solid-state EPR cause intermolecular spin−spin interaction as the reported
G https://doi.org/10.1021/acs.inorgchem.3c00041
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry pubs.acs.org/IC Article

Figure 10. P−E hysteresis loops (red line) and current density−electric field (J−E) (blue line) were measured at 298 K for the drop-casting film of
compounds 1 (a) and 2 (b) by using the double-wave method.

TEMPO-based supramolecular radicals,28 and these com- experienced polar point group (C2v for 1 and Cs for 2)
pounds did not show magnetic regulation due to the structure as a result of the static packing of NH3-TEMPO
disordered/ordered phase transition as the reported radical,17 radical cations at the LTP state to symmetric disordered
either. The combined experimental and crystal structural structures because of the scissoring motion of NH3-TEMPO
results indicate that the supramolecular radicals show no spin− radical cations at the HTP state, resulting in bistability in
spin interaction in the HTP and LTP and the outcome of the dielectric and SHG optical properties. These two supra-
paramagnetic property. molecular radicals reveal ferroelectric properties and para-
Ferroelectric Measurements. Compounds 1 and 2 magnetic properties as previously reported supramolecular
crystallize in polar point groups of C2v and Cs at 298 K, radicals. Importantly, their bistability in optoelectronic proper-
respectively, which belong to the 10 polar point groups, which ties resulting from their structural phase transitions is first
are the requirements for ferroelectricity.47 The structural phase reported in the supramolecular radicals and makes them
transitions for compounds 1 and 2 belong to the 88 possibly applicable to the functional devices for changing over
ferroelectric Aizu notations, mmmFmm2 and mmmFm, the signal status. This also paves an avenue to explore
respectively, which enable them to initially identify the multifunctional supramolecular radical materials with bist-
ferroelectricity.48 Thus, the ferroelectricity of compounds 1 ability in optical, electronic, and magnetic properties.
and 2 was directly verified by using the double-wave method to
measure their P−E hysteresis loops. Since their crystals are too
small to mount electrodes on, drop-cast films from their
■ ASSOCIATED CONTENT
* Supporting Information
sı
solution in DMF were used for the measurements. As shown in
Figure 10a, a typical current density−electric field (J−E) curve The Supporting Information is available free of charge at
with two opposite peaks was observed in the data collected at https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c00041.
298 K. This result corresponds to two stable states with Synthetic procedures, NMR data, crystal cell parameters,
opposite polarities. The P−E hysteresis loop was obtained crystal motifs, thermogravimetric analysis, etc (PDF)
from the J−E curve by integrating the polarization switching
current. As observed in the data, the saturated polarization (Ps) Accession Codes
and coercive electric field (Ec) were determined to be 6.7 μC· CCDC 2145358−2145362 and 2236142−2236143 contain
cm−2 and 45 kV·cm−1 for compound 1, respectively. Its the supplementary crystallographic data for this paper. These
saturated polarization value is similar to that of the reported data can be obtained free of charge via www.ccdc.cam.ac.uk/
supramolecular radical [(NH3-TEMPO)(18-crown-6)][ReO4] data_request/cif, or by emailing [email protected].
and also similar to the theoretical value of 6.6 μC·cm−2 uk, or by contacting The Cambridge Crystallographic Data
calculated by the same method mentioned in the literature Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44
in the Supporting Information 31 according to the crystal 1223 336033.
structure at 298 K. Figure 10b gives Ps and Ec values of 4.0 μC·
cm−2 and 78 kV cm−1 for compound 2, respectively. The
saturated polarization is smaller than that of the theoretical
■ AUTHOR INFORMATION
Corresponding Authors
value of 6.7 μC·cm−2 calculated according to the crystal
Yongfa Xie − School of Chemistry and Chemical Engineering,
structure at 298 K. Although 1 and 2 crystallize in polar point
Nanchang University, Nanchang 330031, China;
groups, regrettably, only compound 1 found a small piezo-
orcid.org/0000-0001-5004-5483; Email: xieyf@
electric response d33 of 1.0 pC·N−1 along the proximity of the
ncu.edu.cn
[001] direction of the crystal at room temperature.
Guangjin Hou − State Key Laboratory of Catalysis, Dalian

■ CONCLUSIONS
In conclusion, three novel supramolecular radical molecules 1,
National Laboratory for Clean Energy, 2011-Collaborative
Innovation Center of Chemistry for Energy Materials, Dalian
Institute of Chemical Physics, Chinese Academy of Sciences,
2, and 3 were synthesized, and their structures were confirmed Dalian 116023, China; orcid.org/0000-0001-8216-
by single-crystal XRD, PXRD, NMR, and elemental analysis. 863X; Email: [email protected]
Compounds 1 and 2 show high-temperature phase transitions Hu Cai − School of Chemistry and Chemical Engineering,
around 382 and 383 K, respectively. Their phase transition Nanchang University, Nanchang 330031, China;
H https://doi.org/10.1021/acs.inorgchem.3c00041
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry pubs.acs.org/IC Article

orcid.org/0000-0003-2372-3319; Email: caihu@ Symmetries and Homochirality. Acc. Chem. Res. 2019, 52, 1928−
ncu.edu.cn 1938.
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Teng-Fei Li − School of Chemistry and Chemical Engineering, Hopkins, E.; Ihlefeld, J. F. Voltage-Controlled Bistable Thermal
Nanchang University, Nanchang 330031, China Conductivity in Suspended Ferroelectric Thin-Film Membranes. ACS
Wei Chen − School of Chemistry and Chemical Engineering, Appl. Mater. Interfaces 2018, 10, 25493−25501.
Nanchang University, Nanchang 330031, China (7) Meng, Y. S.; Jiang, S. D.; Wang, B. W.; Gao, S. Understanding
the Magnetic Anisotropy toward Single-Ion Magnets. Acc. Chem. Res.
Lixin Liang − State Key Laboratory of Catalysis, Dalian
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Dalian 116023, China (9) Chen, Z. X.; Li, Y.; Huang, F. Persistent and Stable Organic
Hui-Peng Lv − Ordered Matter Science Research Center, Radicals: Design, Synthesis, and Applications. Chem 2021, 7, 288−
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Qing Liu − School of Chemistry and Chemical Engineering, (10) Yao, Z. S.; Yamamoto, K.; Cai, H. L.; Takahashi, K.; Sato, O.
Nanchang University, Nanchang 330031, China Above room temperature organic ferroelectrics: diprotonated 1, 4-
Yin-Shan Meng − State Key Laboratory of Fine Chemicals, diazabicyclo [2.2.2] octane shifts between two 2-chlorobenzoates. J.
Dalian University of Technology, Dalian 116024, China; Am. Chem. Soc. 2016, 138, 12005−12008.
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orcid.org/0000-0001-9963-4596
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Complete contact information is available at: 4980−4984.
https://pubs.acs.org/10.1021/acs.inorgchem.3c00041 (12) Morita, Y.; Suzuki, S.; Fukui, K.; Nakazawa, S.; Kitagawa, H.;
Kishida, H.; Okamoto, H.; Naito, A.; Sekine, A.; Ohashi, Y.; Shiro,
Author Contributions M.; Sasaki, K.; Shiomi, D.; Sato, K.; Takui, T.; Nakasuji, K.
Y.F.X. designed the materials, offered the foundation, and Thermochromism in an organic crystal based on the coexistence of
wrote the manuscript; T.-F.L. synthesized the radicals; W.C. σ-and π-dimers. Nat. Mater. 2008, 7, 48−51.
drew the figures and analyzed the NMR spectra; L.L. carried (13) Chi, X.; Itkis, M. E.; Kirschbaum, K.; Pinkerton, A. A.; Oakley,
R. T.; Cordes, A. W.; Haddon, R. C. Dimeric phenalenyl-based
out the solid-state NMR spectra; H.P.L. performed ferro-
neutral radical molecular conductors. J. Am. Chem. Soc. 2001, 123,
electric measurement; Q.L. solved the crystal structures; Y.- 4041−4048.
S.M. performed magnetic property and EPR measurements; (14) Miller, J. S. Bistable Electrical, Optical, and Magnetic Behavior
G.H. analyzed the solid-state NMR spectra and offered in a Molecule-Based Material. Angew. Chem., Int. Ed. 2003, 42, 27−29.
suggestion; and H.C. offered the foundation and suggestion. (15) Paul, A.; Gupta, A.; Konar, S. Magnetic Transition in Organic
Funding Radicals: The Crystal Engineering Aspects. Cryst. Growth Des. 2021,
The financial supports from the National Nature Science 21, 5473−5489.
Foundation of China (Grants Nos. 22065023, 21905127, (16) Deumal, M.; Vela, S.; Fumanal, M.; Ribas-Arino, J.; Novoa, J. J.
21861026, and 22075123) and the Natural Science Founda- Insights into the magnetism and phase transitions of organic radical-
based materials. J. Mater. Chem. C 2021, 9, 10624−10646.
tion of Jiangxi, China (20212BAB203029) are gratefully (17) Paul, A.; Nasani, R.; Mondal, A.; Roy, S.; Vela, S.; Konar, S.
acknowledged. Reversible Magnetic Transition in a Bench-Stable Radical Cation
Notes Triggered by Structural Transition in the Magnetically Silent
The authors declare no competing financial interest. Counteranion. Cryst. Growth Des. 2020, 20, 6296−6301.

■ ACKNOWLEDGMENTS
The authors would like to thank Dr. Chun-Hai Wang
(18) Preuss, K. E. Metal-radical coordination complexes of thiazyl
and selenazyl ligands. Coord. Chem. Rev. 2015, 289−290, 49−61.
(19) Mills, M. B.; Wohlhauser, T.; Stein, B.; Verduyn, W. R.; Song,
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(Northwestern Polytechnical University) for indexing the Magnetic bistability in crystalline organic radicals: the interplay of H-
crystal structures from PXRD data. The authors would like bonding, pancake bonding, and electrostatics in 4-(2′-benzimidazol-
to thank Shiyanjia Lab (www.shiyanjia.com) for the measure- yl)-1, 2, 3, 5-dithiadiazolyl. J. Am. Chem. Soc. 2018, 140, 16904−
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