The effect of electron-withdrawing substituents in asymmetric anthracene derivative semiconductors

Article abstract of DOI:10.1039/d0tc05824f

Three anthracene derivatives, referred to as 2-phenyl anthracene (Ph-Ant), 2-thiazole anthracene (TZ-Ant), and 2-pentafluorophenyl anthracene (F5Ph-Ant), were designed and synthesized to reveal the effects of the electron-withdrawing substituents on the molecular packing structure and photoelectric properties of the anthracene core. As the electron-withdrawing abilities of the substituents increased, the molecular structures of the three semiconductors showed a progressive deterioration in intermolecular interactions and molecular accumulation, and the photoelectric properties became worse. Interestingly, the energy levels of the three semiconductors showed gradually decreasing changes with an enhancement of the electron-withdrawing abilities of the substituents, indicating a possible strategy for fabricating n-type anthracene derivative semiconductor materials.

Full text of DOI:10.1039/d0tc05824f

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Materials Chemistry C
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PAPER
The effect of electron-withdrawing substituents
in asymmetric anthracene derivative
semiconductors†
Cite this: J. Mater. Chem. C, 2021,
9, 4217
Si Liu,‡a Lei Zheng,‡a Mingxi Chen,a Yajing Sun,a Peng Wang,a Shuyu Li,a
ab
Hongnan Wu,a Xiaotao Zhang *a and Wenping Hu
Three anthracene derivatives, referred to as 2-phenyl anthracene (Ph-Ant), 2-thiazole anthracene (TZ-Ant),
and 2-pentafluorophenyl anthracene (F5Ph-Ant), were designed and synthesized to reveal the effects of
the electron-withdrawing substituents on the molecular packing structure and photoelectric properties of
the anthracene core. As the electron-withdrawing abilities of the substituents increased, the molecular
structures of the three semiconductors showed a progressive deterioration in intermolecular interactions
and molecular accumulation, and the photoelectric properties became worse. Interestingly, the energy
levels of the three semiconductors showed gradually decreasing changes with an enhancement of the
electron-withdrawing abilities of the substituents, indicating a possible strategy for fabricating n-type
anthracene derivative semiconductor materials.
Received 11th December 2020,
Accepted 21st February 2021
DOI: 10.1039/d0tc05824f
rsc.li/materials-c
some substituents to the anthracene core in order to extend the
p-conjugation system and modulate the molecular packing to
Introduction
Organic semiconductor materials, which are mainly applied in improve the charge transport properties.18 To date, a variety
the fields of organic solar cells (OSCs),1–3 organic field effect of anthracene derivatives have been designed and developed
transistors (OFETs),4–6 and organic light-emitting diodes for high-performance field effect transistors.19–25 The 2- or
(OLEDs),7–9 have attracted considerable attention.10 Among 2,6-position anthracene derivatives are considered to be the
the diverse organic semiconductor materials reported to date, most promising materials for use in anthracene derivative
anthracene is a hot topic that has been continuously researched semiconductors and have achieved remarkable results owing
and modified by scientists since it was first reported as an to the effective molecular conjugation and molecular packing.
organic semiconductor to study electrical conductivity in For example, the famous molecule modified using phenyl,
1953.11–13 On the one hand, the characteristics of the high known as 2,6-diphenyl anthracene (2,6-DPA), possesses a hole
fluorescence quantum efficiency makes anthracene a promising mobility that can reach 34 cm2 Vꢀ1 sꢀ1 as a result of the short-
building block for use in OLEDs.14–16 On the other hand, the range molecular distance (2.85 Å) and the dense molecular
conjugated and rigid structure of anthracene provides it with packing.20 Li and co-workers designed and synthesized
charge transport properties suitable for application in field effect 2-naphthyl anthracene (NaAnt), the structure of which is almost
transistors. However, the small p-conjugation of anthracene results planar with a small torsion angle of 0.531 between the naphthalene
in a poor field-effect behavior, resulting in only 0.02 cm2 Vꢀ1 sꢀ1 of ring and the anthracene skeleton, and found that it exhibits a
the field-effect mobility.17 Therefore, researchers have introduced maximum mobility of 1.1 cm2 Vꢀ1 sꢀ1 and a high fluorescent
quantum efficiency of 40.3% in the solid state.21 In addition to
extending the p-conjugation and improving the molecular packing,
the introduction of substituents can also regulate energy levels.
a Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University,
Tianjin 300072, China. E-mail: zhangxt@tju.edu.cn
To date, most studies have focused on introducing electron-
donating substituents (thienyl, phenyl, naphthyl, etc.) into the
anthracene skeleton to realize the functionalization of novel
anthracene derivatives. However, there are few studies and reports
on the use of electron withdrawing groups to modify anthracene
towards expected n-type molecules. Therefore, it is necessary to
investigate the effect of the molecular stacking and photoelectric
properties using electron withdrawing groups on the anthracene
b Joint School of National University of Singapore and Tianjin University,
International Campus of Tianjin University, Binhai New City, Fuzhou 350207,
China
† Electronic supplementary information (ESI) available: Crystallographic infor-
mation for TZ-Ant and F5Ph-Ant; transfer characteristics of FETs based on Ph-Ant
and TZ-Ant; AFM characterization of Ph-Ant and TZ-Ant thin films; and CIF files
for TZ-Ant and F5Ph-Ant. CCDC 2033809 and 2033782. For ESI and crystal-
lographic data in CIF or other electronic format see DOI: 10.1039/d0tc05824f
‡ The authors contributed equally to this work.
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skeleton in order to further understand the structure–property– out using Olex2 software. Atomic force microscopy (AFM) images
mobility relationship. were obtained using a Digital Instruments Nanoscope III atomic
In this paper, the effect of three electron-withdrawing sub- force microscope in air.
stituents on the molecular packing structure and photoelectric
Materials
properties of the anthracene core are systematically studied,
these are called 2-phenyl anthracene (Ph-Ant), 2-thiazole anthracene Ph-Ant was synthesized by following the procedures previously
(TZ-Ant) and 2-pentafluorophenyl anthracene (F5Ph-Ant). With the reported.26 F5Ph-Ant was synthesized as follows, to a dry 25 mL
enhancement of the electron-withdrawing ability in these sub- reaction flask with a stir bar, 2-bromoanthracene 100 mg
stituents (phenyl o thiazolyl o pentafluorophenyl), the energy (0.39 mmol), pentafluorophenylboronic acid 95.4 mg (0.45 mmol),
levels of the semiconductors show a gradually decreasing trend CsF 134 mg (0.88 mmol), Ag2O 109 mg (0.47 mmol), Pd2(dba)3 18
which may indicate a feasible strategy to fabricate n-type materials. mg (0.02 mmol) and P(t-Bu)3-HBF4 17 mg (0.06 mmol) were
Moreover, the intermolecular interaction becomes weaker and added. This was then vented three times with nitrogen. Then,
the molecular accumulation becomes more loose, owing to the DMF (4 mL) that had been degassed with nitrogen was added to
increasing effect of the electron-withdrawing ability. The evolu- the reaction flask. The mixture was stirred at 100 1C for 24 h. After
tion of the three molecular structures is based on classic the reaction, the mixture was filtered through a pad of Celite, and
herringbone packing (Ph-Ant), changing to herringbone packing washed with CH2Cl2. The filtrate was then washed with water and
with a slight slip (TZ-Ant), and then to a similar ‘‘face to face’’ the organic phase was collected before being dried over anhy-
stacking (F5Ph-Ant). The field-effect mobility of the three materials drous sodium sulfate and the solvent removed. After column
are 0.2 cm2 Vꢀ1 sꢀ1 (Ph-Ant), 0.05 cm2 Vꢀ1 sꢀ1 (TZ-Ant) and chromatography (hexanes), 67 mg (50%) of a yellow solid was
0 cm2 Vꢀ1 sꢀ1 (F5Ph-Ant), respectively, which is consistent with obtained. 1H NMR (400 MHz, DMSO-d6) d 8.70 (d, 2H), 8.33–8.24
the results of their molecular structures and the theoretical (m, 2H), 8.15 (d, 2H), 7.64–7.54 (m, 3H). 19F NMR (376 MHz,
calculations. Clearly, our work may provide some useful guidance DMSO-d6) d ꢀ143.17 (dd, J = 24.6, 7.8 Hz, 2F), ꢀ155.88 (d, J = 21.9
for revealing the roles of the electron-withdrawing substituents in Hz, 1F), ꢀ162.54 (dd, J = 22.8, 7.4 Hz, 2F). MS (EI) m/z: 344 [M+].
the design and synthesis of anthracene derivative semiconductors.
TZ-Ant was synthesized in two steps: (i) 2-anthraceneborate was
prepared according to previously reported literature procedure.27
(ii) To a dry 50 mL reaction flask with a stir bar, 2-bromo-1,3-
thiazole 100 mg (0.61 mmol), 2-anthraceneborate 155 mg
(0.51 mmol), K2CO3 211 mg (1.53 mmol), and Pd(dppf)Cl2
37 mg (0.05 mmol) were added, this was then vented three times
with nitrogen. Then, 1,4-dioxane (4 mL) and H2O (2 mL), which
had been degassed with nitrogen, were added to the reaction
flask. The mixture was stirred at 100 1C for 16 h. After the
reaction, the mixture was filtered through a pad of Celite, and
washed with CH2Cl2. The filtrate was then washed with water
and the organic phase was collected, it was then dried over
anhydrous sodium sulfate and the solvent was removed. After
column chromatography (hexanes), 103 mg (77%) of a yellow
Experimental
General method
All reagents and chemicals were received from commercial
resources and used directly without further purification. Bruker
400 and 600 NMR spectrometer were used to record the 1H, 13
C
and 19F NMR spectra. The deuterated reagents used for Ph-Ant
and TZ-Ant were CDCl3 with TMS (d 0.00 ppm). F5Ph-Ant was
placed in DMSO-D6 with TMS (d 0.00 ppm). Thermal gravimetric
analysis curves (TGA) were obtained on a METTLER TOLEDO
TGA2 apparatus with a heating rate of 10 1C minꢀ1 in nitrogen.
Ultraviolet-visible (UV-Vis) spectra were measured on a SHI-
MADZU UV-3600 UV-Vis-NIR spectrophotometer (Japan). Photo-
luminescence (PL) spectra were recorded on a HITACHI F-7000
spectrofluorometer (Japan). Fluorescence quantum yield was
measured using an Edinburgh Instruments FLS 1000 spectrometer.
Cyclic voltammetry (CV) curves were scanned on a CHI660C
electrochemistry station in dry CH2Cl2,tetrabutlyammonium
hexafluorophosphate (Bu4NPF6) was used as an electrolyte
(0.1M) and ferrocene was used as an internal standard. Glassy
carbon, Pt wire and Ag/AgCl were used as the working, counter,
and reference electrodes, respectively. The highest occupied
molecular orbital (HOMO) energy levels were estimated according
to the onsets of the oxidative peaks and the empirical formula
1
solid was obtained. H NMR (600 MHz, CDCl3) d 8.63 (s, 1H),
8.52 (s, 1H), 8.43 (s, 1H), 8.08 (d, 2H), 8.04–7.99 (m, 2H), 7.95
(d, 1H), 7.53–7.47 (m, 2H), 7.40 (d, 1H). 13C NMR (101 MHz,
CDCl3) d 168.65, 144.03, 132.53, 132.38, 131.89, 131.32, 130.53,
129.25, 128.40, 128.37, 127.56, 126.48, 126.48, 126.14, 125.97,
123.77, 119.11. HRMS: [M + H]+ = 262.0677 (calcd 262.0685).
Fabrication of the devices
A two-zone horizontal tube furnace was employed for physical
vapor deposition (PVT), and the system was evacuated using a
mechanical pump, which was kept at 17 Pa. The quartz boat with
the Ph-Ant, TZ-Ant or F5Ph-Ant powder of the raw materials was
placed in the high-temperature zone (100, 95 and 90 1C) for
2.5 h. High-purity argon was used as the carrier gas (20 sccm).
ꢀ
ꢁ
EHOMO ¼ ꢀ Eooxnset þ 4:8 þ EFonc=seFtcþ eV. The lowest unoccupied
molecular orbital (LUMO) energy level was calculated by using For the fabrication of the organic single crystal field effect
the bandgap and the HOMO level (ELUMO = EHOMO + Eg). X-ray transistors (OSCs-FETs): first, the organic semiconductor
diffraction crystallography data were collected on a Rigaku Super- micro-nano crystals were grown on an octadecyltrichlorosilane-
nova CCD diffractometer with a Cu-Ka source (l = 0.154 nm) at treated (OTS) SiO2 (300 nm)/Si substrate using the PVT method.
293 K. The structure and refinement determinations were carried Then, the source electrode and drain electrode were applied by
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using the ‘‘gold-layer sticking’’ technique.28 For fabrication of
the organic thin film transistor (OTFTs): thin films of the organic
semiconductor were grown that were about 40 nm in thickness
using vacuum deposition at a deposition speed of 0.1–0.5 Å sꢀ1
on OTS modified SiO2/Si substrates. The field-effect transistor
characteristic measurements were carried out under ambient
conditions on a Keithley 4200 SCS and Micromanipulator 6150
probe station (USA). The mobility was extracted from the satura-
tion region by using the equation IDS = (W/2L)Cim(VG ꢀ VT)2.
Results and discussion
Synthesis
The target compounds (Ph-Ant, TZ-Ant, and F5Ph-Ant) were
prepared using the Suzuki coupling reaction. The synthetic
routes are shown in Scheme 1. A commercially available
material, 2-bromoanthracene, was used as the raw material
for all reactions. 2-Anthraceneborate was synthesized according
to the reported literature procedure.27 The yields of Ph-Ant and
TZ-Ant can reach above 70%. For F5Ph-Ant, pentafluorophenyl-
boronic acid (C6F5B(OH)2) is a highly electron-deficient aryl-
boronic acid, but the yield can reach 50% through the
improved reaction conditions mentioned in the literature.29
All products are yellow solids and were characterized using
NMR and mass spectrometry.
Fig. 1 (a) TGA curves of Ph-Ant, TZ-Ant, and F5Ph-Ant. UV-vis absorption
spectra of compounds in solution (b) and as solids (c). PL spectra of
compounds in solution (d) and as solids (e). (f) Cyclic voltammogram curves
for Ph-Ant, TZ-Ant, and F5Ph-Ant.
Thermal, optical, and electrochemical properties
In a nitrogen flow, the TGA curves were measured to investigate
the thermal stabilities of the three compounds, as shown in
Fig. 1a. The decomposition temperatures (Td, 5% weight loss)
of Ph-Ant, TZ-Ant, and F5Ph-Ant are 248, 240 and 214 1C. The
Table 1 Physicochemical properties of the three materials
Sol
Compound
TGA (1C)
l
(nm)
Eg (eV)
PLQY (%)
max
decomposition temperature of all compounds is above 200 1C, Ph-Ant
246 1C
241 1C
215 1C
279
301
258
2.97
2.90
3.00
28.87
10.89
18.21
TZ-Ant
indicating their high thermal stability.
F5Ph-Ant
The optical properties of the three compounds were studied
using UV-Vis absorption spectroscopy and fluorescence emission
spectroscopy in a dilute solution of CH2Cl2 (10ꢀ5 M) and the
atoms owing to their strong electronegativity, resulting in an
increase in the electrostatic repulsion and steric hindrance
between the pentafluorophenyl group and the anthracene core,
which reduces the degree of conjugation. This also indicates that
the structural planarity of F5Ph-Ant is not as good as that of
Ph-Ant. The absorption peaks in the solid state showed a bath-
ochromic shift, as compared to that in solution, indicating the
formation of J-aggregates in the solid form. The optical energy level
band gaps (Eg) of the compounds calculated from their respective
initial absorption wavelengths were ꢀ2.97, ꢀ2.90, and ꢀ3.00 eV
for Ph-Ant, TZ-Ant and F5Ph-Ant. The fluorescence emission peaks
range from about 400 to 540 nm, mainly showing a blue light
emission with photoluminescence quantum yield (PLQY) values of
28.87%, 10.89%, and 18.21% for Ph-Ant, TZ-Ant, and F5Ph-Ant in
the solid state.
crystal powder state. The resulting spectra are shown in Fig. 1b–e
and the corresponding values are listed in Table 1. The maximum
absorption peaks of Ph-Ant, TZ-Ant and F5Ph-Ant are 279, 301, and
258 nm in solution. In comparison with Ph-Ant, the absorption
peaks of TZ-Ant are red-shifted; this reveals the better conjugation
of the molecules when the thiazolyl group is introduced. This can
also be explained by the torsion angle between the substituent and
the anthracene skeleton, which is discussed in the section entitled
‘‘Crystal structure and molecular packing’’. F5Ph-Ant showed a
blue-shift, fluorine atoms have more electrons than hydrogen
Cyclic voltammetry (CV) measurements in dry dichloromethane
(CH2Cl2) were performed to explore the electrochemical properties
and oxidative stability of these compounds, as shown in Fig. 1f.
Using ferrocene as the internal standard, the HOMO levels for
compounds Ph-Ant, TZ-Ant, F5Ph-Ant were respectively calculated
Scheme 1 Synthetic routes to Ph-Ant, F5Ph-Ant, and TZ-Ant.
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Fig. 2 The frontier molecular orbitals calculated using DFT theory and the
energy levels calculated using theoretical (black) and experimental tests
(red).
to be ꢀ5.61, ꢀ5.60, and ꢀ5.75 eV according to the onset of the
oxidation peaks. The LUMO energy levels for the anthracene
derivatives were Ph-Ant: ꢀ2.64 eV, TZ-Ant: ꢀ2.70 eV, and F5Ph-
Ant: ꢀ2.75 eV, which were calculated from the band gap and the
HOMO energy level (ELUMO = EHOMO + Eg). These values indicate
that the materials have a good ambient stability, which is con-
sistent with the wide band gaps. Compared with the other two
anthracene derivatives, F5Ph-Ant has the deepest HOMO level
owing to the strong electron-withdrawing ability of the sub-
stituents. Thiazolyl is a weaker electron-withdrawing group,
and the LUMO energy level of TZ-Ant also showed a decrease.
In addition, the frontier molecular orbitals and energy levels of
the three compounds were calculated using density functional
theory (DFT) calculations, see Fig. 2. The energy levels calcu-
lated using DFT were ꢀ5.192, ꢀ5.271, and ꢀ5.440 eV (HOMO)
and ꢀ1.715, ꢀ1.942, and ꢀ1.966 eV (LUMO) for Ph-Ant, TZ-Ant,
and F5Ph-Ant. Showing a slight decreasing trend, which is in
line with that obtained using cyclic voltammetry. The energy
levels of the three materials did not achieve a low LUMO energy
level (ꢀ3 to ꢀ4.5 eV) for the n-type semiconductor materials,
but the energy levels gradually decreased with the enhance-
ment of the electron withdrawing ability of the substituents,
indicating that this strategy is feasible.
Fig. 3 Single-crystal structures, packing motifs, and short contacts for
Ph-Ant (a–c), TZ-Ant (d–f), and F5Ph-Ant (g–i).
a torsion angle of 6.171 between the benzene ring and the
anthracene core and are packed in a typical herringbone
arrangement. Multiple C–H–p interactions with distances
Crystal structure and molecular packing
The crystal structure and molecular packing of the three between 2.339–2.868 Å are observed for each Ph-Ant molecule
materials were analyzed and compared to study the influence with its four neighboring molecules (Fig. 3c). The information
of the substituents on the structure. High-quality single crystals indicates that it has good charge transport properties.20–23 For
of TZ-Ant and F5Ph-Ant were grown by slowly volatilizing the TZ-Ant, the crystal system is orthorhombic and the space group
saturated ethyl acetate solution of TZ-Ant and the saturated is Pna21. As shown in Fig. 3d, the TZ-Ant molecule is almost flat
petroleum ether solution of F5Ph-Ant for X-ray diffraction with a small torsion of 1.861 between the substituent and the
analysis (TZ-Ant, CCDC: 2033809; F5Ph- Ant, CCDC: 2033782). anthracene skeleton, which indicates that it has a better
The crystal data for Ph-Ant (CCDC: 1435446) were obtained planarity than Ph-Ant and corresponds to the ultraviolet
from the literature.30 The crystallographic data for TZ-Ant and absorption red-shift mentioned above. The central molecule
F5Ph-ant are presented in Table S1 (ESI†). The crystal structure interacts with four adjacent molecules, two types of C–H–p
and molecular packing of Ph-Ant, TZ-Ant, and F5Ph-Ant are interactions are observed at distances of 2.821 and 2.882 Å, see
shown in Fig. 3. Fig. 3a and b shows that Ph-Ant molecules have Fig. 3f. TZ-Ant adopts a herringbone stacking mode (Fig. 3e),
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Fig. 4 Illustrations of the charge transport pathways and transport integrals of the holes and the intermolecular distances between the two parallel
planes of (a) Ph-Ant, (b) TZ-Ant, and (c) F5Ph-Ant.
which is different from that of Ph-Ant; there is a slip along the Charge transport properties of OFETs
long axis between the central molecule and the neighboring
Bottom-gate top-contact OFETs (Fig. 5a and Fig. S3a, ESI†)
based on the above three semiconductors were fabricated to
study the charge transport properties. The thin-film-based
molecules (Fig. S1d, ESI†), which reduces the ‘‘edge-to-face’’
overlap and adversely effects the charge transfer properties.31
The X-ray crystallographic results show that F5Ph-Ant belongs
OFETs based on Ph-Ant and TZ-Ant exhibited a typical p-type
to the orthorhombic Pna21 space group. A similar accumulation
mobility of 0.087 and 7 ꢁ 10ꢀ5 cm2 Vꢀ1
s
ꢀ1, respectively, as
of ‘‘face to face’’ was observed, see Fig. 3h and Fig. S1 (ESI†).
However, there is a large torsion angle of 46.831 (Fig. 3g)
between the pentafluorophenyl group and the anthracene core in
F5Ph-Ant, therefore the molecular planarity and p-conjugation are
far less than that of Ph-Ant and TZ-Ant. The large twist angle not
only effects the planarity of the molecules, but also causes the
molecular packing to appear looser and the intermolecular inter-
action to decrease. As shown in Fig. 3i, F5Ph-Ant only interacts with
two surrounding molecules with a C–H–p interaction distance of
2.805 Å and a C–C interaction distance of 3.341 Å. The loose
accumulation of molecules may have negative effects. Based on
the Gaussian software suite at the B3LYP/6-31G(d)/LANL2DZ level of
theory, the values of the hole (Vh) transport integrals and inter-
molecular distances between the two parallel planes of three
materials are shown in Fig. 4. The decreasing Vh are consistent
with the deteriorative molecular structures.
shown in Fig. S2 (ESI†). To further determine the intrinsic
charge transport efficiency of semiconductors, single-crystal-
based OFETs were successfully constructed onto the OTS
modified SiO2/Si substrates by using the ‘‘gold-layer sticking’’
technique.
Fig. 5b and c shows the mobility of Ph-Ant reached
0.2 cm2 Vꢀ1 sꢀ1 with a current on/off ratio of 106. For the
TZ-Ant device, a lower mobility of 0.005 cm2 Vꢀ1 sꢀ1 with a
current on/off ratio of 105 was obtained, and the transfer curve
is shown in Fig. S3b (ESI†). In contrast, the decreasing mobility of
the TZ-Ant device is caused by the deteriorative crystal structure
and packing, compared to that of Ph-Ant. In our study, the F5Ph-
Ant devices do not show normal field-effect properties, this may
be due to the poor molecular planarity, unsatisfactory molecular
stacking and weak molecular interaction caused by the large
torsion angle. Clearly, the field-effect mobility based on thin films
and the single crystals all showed decreasing variation trends
with the increasing electron-withdrawing ability in the asym-
metric anthracene derivative semiconductors with different elec-
tron withdrawing substituents (Fig. 5d).
Conclusions
In summary, three 2-substituted anthracene derivatives were
synthesized that were modified with three different electron-
withdrawing substituents: TZ-Ant, Ph-Ant, and F5Ph-Ant. It was
found that the quality of the molecular packing structures of
the anthracene derivatives and the photoelectric properties
were significantly decreased with an increase in the electron-
withdrawing abilities. Interestingly, the energy levels of the
three compounds also showed a decreasing trend with an
increase in the electron-withdrawing abilities, which may provide
useful guidance for the design and synthesis of n-type anthracene
derivative semiconductors. In addition, single-crystal-based OFETs
were successfully constructed to further reveal the intrinsic electrical
properties of the above three materials, the mobility of which
Fig. 5 (a) A schematic diagram of the OSC-FET. (b) Typical transfer and
(c) output curves of the single-crystal-based transistor of Ph-Ant. (d) Mobilities
of the three materials based on single-crystal (black) and thin-film (red) field-
effect transistors.
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decreased from 0.2 cm2 Vꢀ1 sꢀ1 to 0, which was consistent with
the results obtained from their molecular structures and theore-
tical calculations.
14 J. Liu, L. Meng, W. Zhu, C. Zhang, H. Zhang, Y. Yao,
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16 J. Zhang, B. Xu, J. Chen, S. Ma, Y. Dong, L. Wang, B. Li, L. Ye
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17 A. N. Aleshin, J. Y. Lee, S. W. Chu, J. S. Kim and Y. W. Park,
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The authors acknowledge financial support from the National
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Science Foundation of China (91833306, 21875158, 51633006,
and 51733004).
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