Aggregation-induced photodimerization of an alkynylpyrene derivative as a photoresponsive fluorescent ink

Article abstract of DOI:10.1039/c9tc03786a

Smart luminescent materials can substantially alter their physicochemical properties with various stimuli and thus have long been a point of interest for the development and manufacture of various commodities. In particular, photoresponsive materials have

Full text of DOI:10.1039/c9tc03786a

Showcasing research from National Engineering Research
Center for Colloidal Materials, Shandong University, Jinan,
China.
As featured in:
Volume
7 Number 44 28 November 2019 Pages 13649–13996
Journal of
Aggregation-induced photodimerization of an alkynylpyrene
derivative as a photoresponsive fluorescent ink
Materials Chemistry C
Materials for optical, magnetic and electronic devices
rsc.li/materials-c
By rationally introducing multiple noncovalent interactions
into a well-designed amphiphilic alkynylpyrene derivative,
an aggregation-induced photochemical reaction has been
successfully achieved. This platform can act as a smart
luminescent system towards confidential information
encryption and decryption by photolithography and
inkjet printing techniques.
ISSN 2050-7526
PAPER
Carmen Tiseanu et al.
Effects of local symmetry on upconversion emission
mechanisms under pulsed excitation
See Xing-Dong Xu et al.,
J. Mater. Chem. C, 2019, 7, 13786.
rsc.li/materials-c
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Aggregation-induced photodimerization of an
alkynylpyrene derivative as a photoresponsive
fluorescent ink†
Cite this: J. Mater. Chem. C, 2019,
7, 13786
Junying Zhang, Shao-Xiong Tang, Rong Fu, Xing-Dong Xu * and
Shengyu Feng
Smart luminescent materials can substantially alter their physicochemical properties with various stimuli
and thus have long been a point of interest for the development and manufacture of various
commodities. In particular, photoresponsive materials have seen much commercial success as sensors
and for applications in the paint and coating industry. Herein, we report the design, synthesis, and
material processing of a novel alkynylpyrene derivative. The aggregation behavior of this compound can
be fine tuned in response to different conditions, such as solvent polarity, concentration, and ratio of
good solvents to poor solvents. In addition, the concentration-dependent 1H NMR spectroscopic study
and single crystal structure of the model compound revealed that multiple weak intermolecular
interactions might be responsible for the formation of highly ordered aggregates. With the formation of
highly ordered aggregates through molecular self-assembly, photodimerization can be realized
effectively with 400 nm LED irradiation. Owing to the invisible and controlled printable characteristics of
the aggregates and the conversion process of the luminescent material, we have demonstrated that our
platform can act as a smart luminescent system towards confidential information encryption and
decryption with various high-resolution patterns by photolithography and inkjet-printing techniques. In
addition, the inherent molecular packing of the materials allows us to quench the luminescence of the
as-printed characters easily upon blue visible light irradiation and realize the irreversible erasure of the
luminescence signal for multiple information rewritable processes. As a result, the present luminescent
material will find applications in the fields of optical information storage, information security protection,
and erase/rewrite systems and provide a proof-of-principle application.
Received 12th July 2019,
Accepted 3rd October 2019
DOI: 10.1039/c9tc03786a
rsc.li/materials-c
structures in the aggregate state with various stimuli, tunable
luminescence signals can be achieved.
Introduction
In the past few decades, stimuli-responsive luminescent materials
Among all the potential external stimulus strategies, light is
have gained considerable attention due to their smart behavior.1 an ideal trigger since it features high spatio-temporal resolution,
Such smart materials that are capable of undergoing luminescence minimal invasiveness and easy control of wavelength, intensity,
color and intensity changes in response to physical and chemical coverage area, and illumination duration.10 Furthermore, the
stimuli have opened new paths to numerous applications possibility to tune its wavelength and intensity guarantees a
including mechanochromic materials,2 temperature sensors,3 wealth of solutions when photochromic systems are intelligently
pH detectors,4 pressure sensors,5 anti-counterfeiting materials,6 designed.11 As such, supramolecular control of photochemical
etc. So far, a large number of stimuli-responsive luminescent reactions has emerged as an important strategy for the con-
materials including small organic dyes,7 polymers,8 and luminescent struction of smart materials by [2+2] photodimerizations.12
metal–organic frameworks9 have been extensively explored in However, the current scope of supramolecular photochemistry
this field. Through controlling their chemical constitutions or is generally restricted to reactions occurring in the solid state.13
Contrary to this situation, the control of the outcome of inter-
National Engineering Research Center for Colloidal Materials, Key Laboratory of
molecular photochemical reactions in homogeneous solutions
remains a significant challenge. By introduction of multiple
weak interactions, it may be possible to achieve similar topo-
Special Functional Aggregated Materials of Ministry of Education, Shandong
University, Jinan, 250100, Shandong, China. E-mail: xuxd@sdu.edu.cn
† Electronic supplementary information (ESI) available: Details of characterization,
chemical control in solution reactions as is possible in the
solid state.
crystallographic data (CIF) and more measurement data. CCDC 1937449. For ESI and
crystallographic data in CIF or other electronic format see DOI: 10.1039/c9tc03786a
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Among the various building blocks used to construct photo-
Journal of Materials Chemistry C
controlled supramolecular materials, pyrene is a well-known
conventional organic fluorophore that possesses a number of
unique photophysical properties, such as good thermal stability,
high fluorescence quantum yield, long fluorescence lifetime, and
high polarity dependence of the fine structure of its monomer
emission.14 In addition, the transformation between monomer
and excimer with various external stimuli allowed the successful
application of pyrenes in optical switches, smart thermosensors,
functional photoelectric materials, and information storage
media.15–17 For example, Kool and co-workers described a photo-
switchable DNA-based alkynylpyrene excimer dye that visibly
changes fluorescence from green to blue upon UV irradiation.16
Very recently, we also constructed a fluorescent thermometer
based on amphiphilic alkynylpyrene derivatives which exhibits
temperature-dependent ratiometric luminescence between red and
green and showed their potential applications in temperature
gradient distribution and document security.17 However, it is still
a big challenge to realize well-controlled aggregates for a photo-
chemical reaction of a small conjugated pyrene derivative in
aqueous solution via spontaneous self-assembly.
Based on our previous research results on stimuli-responsive
well-controlled aggregates of small organic dyes,18 we herein
designed a novel alkynylpyrene derivative with multiple inter-
molecular noncovalent interactions. The luminescence behavior
can be regulated with an ordered molecule aggregation, which
showed blue to green transformation gradually. The photochemical
reaction has been successfully developed in the aggregate state,
Scheme 1 Chemical structures and graphical representation of photo-
responsive alkynylpyrene derivatives 1 and 1M.
accompanied with purple emission. The effective conversion pro- of 1 in DMSO (1.0 Â 10À5 M, Fig. 1a), which can be assigned to
cess showed potential applications in photolithography and inkjet the charge-transfer transitions induced by J-aggregation.19
printing, allowing us to develop a platform in which tunable Interestingly, the alkynylpyrene derivative exhibited solvent-
supramolecular nanomaterials can be employed as fluorescent dependent emission properties in solution. For example, the
security inks for anti-counterfeiting strategies (Scheme 1).
emission color for 1 changed from blue in dichloromethane to
green in aqueous solution (Fig. 1b). The Stokes’ shifts for 1
consecutively increased, accompanying the disappearance of
their vibronic band, with the increase of the solvent polarity. As
observed above, the alkynylpyrene derivative showed monomer
Results and discussion
The design of the amphiphilic fluorescent compound 1 is based emission in DMSO and excimer emission in water. So, the
on our previous research results on fluorescent structures.18 aggregation behavior of 1 was also studied in the mixed solvent
The structure (Scheme 1) employs a conjugated alkynylpyrene of DMSO and water. As shown in Fig. 1c and Fig S2 in the ESI,†
fluorophore component, chosen due to its good planarity, strong with the increasing water fraction, an obvious decrease of the
fluorescence emission characteristics, significant Stokes shift, high-energy emission intensity was observed. For example,
and sensitive luminescence between the monomer and excimer when the water content was increased to 90%, the emission
states. Appended to the fluorophore component is a glycol-based intensity value of 1 at 440 nm decreased approximately 100-fold
hydrophilic group, which is known for its use in the formation of compared to the starting value. At the same time, excimer
amphiphilic compounds in the solution phase. The synthesis of emission at 505 nm was observed due to the aggregation of 1
an alkynylpyrene complex 1 and 1M is outlined in Scheme S1 (see induced by the decrease of solubility. These spectral changes
ESI†). The resulting molecule was characterized by multiple are consistent with the formation of head-to-tail type aggregates
nuclear NMR spectroscopies (1H, and 13C), and FT-IR and HR-ESI with a slip-stacked geometry according to the previous report.
mass spectroscopy and the results were found to be in full
agreement with its structure.
Furthermore, concentration-dependent 1H NMR spectro-
scopic studies of 1 in CDCl3 were performed to probe the
With the newly designed alkynylpyrene in hand, the aggre- driving forces for the aggregation process (Fig. 2). It was found
gation behaviour of the complex both in solution and on the that the resonance of the protons in the aromatic unit displayed
surface was investigated. Notably, the absorption maximum of an obvious upfield shift upon increasing the concentration
the aqueous solution is slightly red-shifted (ca. 8 nm) and (e.g., Dd = 0.05 ppm for Ha, 0.03 ppm for Hb, 0.27 ppm for Hc,
significantly broadened compared to the absorption spectrum and 0.04 ppm for Hd from 1.0 Â 10À4 M to 1.0 Â 10À3 M),
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Fig. 1 (a) Normalized UV/Vis spectra of 1 in DMSO and in aqueous
solution (1.0 Â 10À5 M); (b) fluorescence emission spectra of 1 in different
solvents (1.0 Â 10À5 M, lex = 340 nm); (c) fluorescence emission spectra
of 1 in DMSO/H2O mixtures with different DMSO fractions at a fixed
concentration (1.0 Â 10À5 M, lex = 340 nm); (d) photoimages of the
luminescent color changes of 1 with different DMSO/H2O ratios (left 70%
DMSO, right 60% DMSO) under a 365 nm handheld UV lamp.
Fig. 3 (a) X-ray crystal structure of a model compound 1M, and (b) the
packing diagram of compound 1M from side view.
model compound 1M were grown by slow vapor evaporation of
the precursor in solution (CH2Cl2/MeOH, 1 : 1) at ambient
temperature for 2–3 days. An ORTEP of compound 1M (Fig. 3)
showed that all of the carbon atoms lay in approximately the
same plane. The packing pattern of compound 1M in the solid
state was also investigated. As shown in Fig. 3b, the pyrene
rings of two adjacent molecules are stacked in a parallel pattern
and the distance between the nearest two pyrene rings in the
adjacent molecules was approximately 3.48 Å, which indicates
the typical p–p interactions between such molecules in the
crystalline state. N–HÁ Á ÁO hydrogen bonds with a distance of
2.13 Å are formed between the two neighbouring amide groups.
These findings suggest that multiple weak intermolecular
interactions may exist in the crystals, which are responsible
for the formation of highly ordered aggregates through mole-
cular self-assembly. The identity of the aggregate (mostly in the
form of oligomers) was also supported by electrospray ioniza-
tion mass spectrometry (ESI-MS) studies of 1M (Fig. S8, ESI†),
Fig. 2 Region of the 1H NMR spectrum (400 MHz, CDCl3, 298 K) of
compound 1 at different concentrations.
indicating the existence of p–p stacking interactions during the in which the presence of dimeric and trimeric species ([M2 +
formation of a supramolecular aggregate. To further corroborate Na]+ and [M3 + Na]+) apart from monomeric species ([M + H]+)
the mechanism of aggregate formation, the Fourier transform was observed. From these results, we infer that the formation
infrared (FT-IR) spectrum of the corresponding aggregate was of molecular aggregates can be achieved in conjuction with
recorded (Fig. S3, ESI†). The N–H band centered at 3319 cmÀ1 is multiple weak interactions including p–p interaction, hydrogen
characteristic of N–H functions involved in hydrogen bonding bonding and other weaker interactions.
interaction.20 The amide I band at 1669 cmÀ1 and the CQO
stretching band at 1586 cmÀ1 show evidence for the hydrogen from compound 1 stimulated us to investigate its self-assembly
bonding network. behavior in aqueous solution by using scanning electron micro-
The nature of multiple intermolecular noncovalent interactions
To further understand the packing property of the alkynyl- scopy (SEM). As demonstrated in Fig. 4a, the self-assembled
pyrene derivative in the aggregate state, single crystals of the amphiphilic derivative 1 exhibits a spherical morphology with a
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reaction between the two unsaturated bonds, which was similar
to Kool and coworkers’ first report.16 The transition ratio is 84.0%
after 10 s irradiation, 95.2% after 30 s irradiation, and 98.7% after
60 s irradiation upon fluorescence quenching at 515 nm, showing
high conversion efficiency. Fig. 5d shows the color change of the
luminescence in the Commission Internationale de L’Eclairage
(CIE) 1931 coordinates chromaticity diagram with different
exposure times. As observed from the CIE coordinates, the
coordinates shift from (0.255, 0.517) to (0.166, 0.032), which
agrees well with the change in emission spectra and a colour
change from green to nearly purple can be seen. Surprisingly,
the photochemical reaction did not give the expected dimeric
complex in a pure DMSO solution with the same concentration,
indicating the importance of ordered molecular packing.
Finally, we have demonstrated the emission patterning by
using the phenomenon of photoinduced emission color change,
as this is often useful in high-level information storage and
security protection applications. Fig. 6 shows that a blue LED
(with wavelengths typically at 400 nm) could be used as a pen to
write symbols freehand on a filter paper fabricated by drop-
casting an aqueous solution of the alkynylpyrene derivative 1.
The regions exposed to the laser beam turned colorless within
60 seconds due to the photochemical reaction of alkynylpyrene,
while the unexposed area retained the original excimer emission
color of 1, producing a pattern with sufficient contrast to be
observed with the naked eye. Fig. 6 shows the fluorescence
images of the papers after irradiation. The characters were
clearly recognizable for the irradiated film after irradiation,
whereas the pattern was scarcely recognizable before irradiation.
The media showed high resolution and good stability under
office light conditions, making the system suitable for applica-
tion in photolithography patterns.
Inkjet printing is a cost effective, readily accessible, high
throughput solution processing method for the deposition and
incorporation of functional materials onto paper substrates.
To demonstrate the behaviour of alkynylpyrene derivative-
based fluorescent hydrochromes in this medium, pristine inks
comprised of 0.01 mM aqueous solution of the amphiphilic
fluorophore were used to fill a conventional inkjet printer ink
cartridge. Images of a brief introduction of Shandong University
and a complicated bamboo pattern were then printed on a
conventional non-fluorescent A4-sized printer paper (Fig. 7).
When visualized under irradiation with 365 nm light, the inkjet
printed design exhibited bright fluorescence emission, which
visually approximated the chromatic behavior of the previously
described compound 1 processed paper.
Fig. 4 (a) SEM image of 1 prepared in a DMSO/H2O mixture (v/v 1 : 99).
Scale bar: 1.0 mm; (b) DLS data of the nanospheres self-assembled from
compound 1 (1.0 Â 10À3 M) with an inset showing the Tyndall effect of
compound 1.
diameter range of 150–300 nm. In addition, the same solution of
compound 1 showed clear evidence of the Tyndall effect (inset in
Fig. 4b), demonstrating the formation of nanoscale aggregates.
Dynamic laser scattering (DLS) examination reveals that the nano-
spheres have a narrow size distribution, showing an average
diameter of 200 nm at a scattering angle of 901 (Fig. 4b).
In general, photochemical [2+2] reactions between two
unsaturated bonds will occur when they are arranged in an
approximately parallel fashion and are separated by less than
4.2 Å.21 Based on the above mentioned research and analysis,
the alkynylpyrene derivative 1 in the aggregate state will be an
ideal candidate for photodimerization. To investigate the
photoreactivity of 1, a sample of the compound was dissolved
in aqueous solution and exposed to a 400 nm light source for
irradiation. The excimer emission band at around 515 nm
present before irradiation immediately decreased and almost
disappeared after 10 seconds (Fig. 5b). Simultaneously, new
bands appeared at 380 and 405 nm, which correspond to the
emission bands of free pyrene. Furthermore, the isosbestic
point at 445 nm was indicative of the selective photodimerization
Benefiting from the good photochemical luminescence
behaviors, the assembly could serve as a photoerasable fluorescence
ink. In a typical test, some characters were written with the aqueous
solution of alkynylpyrene derivative 1 as ink on ordinary white
paper, these characters emitted bright green fluorescence upon
exposure to UV light at 365 nm after being dried in air
(Fig. 8). When irradiated with blue light (400 nm), the characters
disappeared within 1 minute. Interestingly, the erased papers
can be rewritten multiple times without loss in resolution.
These photoerasable properties will enable the application of
Fig. 5 (a) Emission spectra of alkynylpyrene derivative 1 in DMSO solution
over 6 min upon exposure to 400 nm LED light; (b) emission spectra of
alkynylpyrene derivative 1 in aqueous solution over 10 min upon exposure
to 400 nm LED light; (c) time dependence of the ratio of fluorescence
intensity (I515nm/I390nm) of 1; (d) CIE chromaticity diagram showing the time
dependence of the (x, y) color coordinates of 1.
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Fig. 6 (a) Schematic illustration of 1 for photolithography upon 400 nm LED irradiation with a photomask which bears patterns that will be printed onto
a substrate; sample photographs of (b) a square photomask, (c) butterfly pattern and (d) brief introduction of Shandong University.
Fig. 7 Luminescent patterns from alkynylpyrene derivative 1 via inkjet printing. (a) Schematic illustrations of the patterning process from a colorless
aqueous solution of 1; digital images of the printed brief introduction of Shandong University on a commercial parchment paper under (b) ambient light
and (c) a 365 nm UV lamp; (d) a printed complicated bamboo pattern under irradiation with a 365 nm UV lamp.
the aggregate as a novel anticounterfeiting material in which the from potassium hydroxide. All reactions were performed in
information and the state could be effectively written, con- standard glassware under an inert N2 atmosphere. Compounds
cealed, read out, and permanently erased by simply alternating S0 and S1 were prepared according to the reported procedure.22
the irradiation with UV and visible blue light.
Analytical thin-layer chromatography (TLC) was performed on
aluminum sheets, precoated with silica gel 60-F254. Deuterated
solvents (Cambridge Isotope Laboratories) for NMR spectro-
Experimental
General
1
scopic analyses were used as received. H NMR and 13C NMR
spectra were recorded on a Bruker 400 MHz Spectrometer
All reagents and solvents were purchased from commercial at 298 K. The 1H and 13C NMR chemical shifts are reported
sources. THF was distilled from sodium; i-Pr2NH was dried relative to the residual solvent signals. Coupling constants ( J)
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7.99 (d, J = 8.0 Hz, 2H), 7.97 (d, J = 8.0 Hz, 2H), 7.79
(d, J = 8.0 Hz, 2H), 7.63–7.55 (m, 3H); 13C NMR (DMSO-d6,
100 MHz): d = 166.28, 140.38, 135.25, 132.64, 132.25, 131.46,
131.29, 131.02, 129.98, 129.28, 128.94, 128.78, 128.23, 123.93,
124.19, 125.38, 125.45, 126.41, 126.46, 127.25, 127.74, 117.52,
117.67, 120.72, 96.03, 88.18 ppm; HR-ESI-MS: m/z calcd for
C
31H20NO: 422.1545 [M + H]+; found: 422.1500; C62H38N2NaO2:
865.2831 [2M + Na]+; found: 865.2712; C93H57N3NaO3: 1286.4298
[3M + Na]+; found: 1286.4052.
Compound 1. Pale yellow oil. Yield: 79.8%. Rf = 0.60
(dichloromethane/petroleum ether 3 : 1); 1H NMR (CDCl3,
400 MHz): d = 8.68 (d, J = 8.0 Hz, 1H), 8.44 (s, 1H), 8.25–8.19
(m, 4H), 8.15–8.02 (m, 4H), 7.79 (d, J = 8.0 Hz, 2H), 7.72
(d, J = 8.0 Hz, 2H), 7.28 (s, 2H), 4.28–4.24 (m, 6H), 3.88–3.80
(m, 6H), 3.75–3.63 (m, 18H), 3.56–3.52 (m, 6H), 3.38 (s, 3H),
3.34 (s, 6H); 13C NMR (CDCl3, 100 MHz): d = 165.46, 152.56,
142.08, 138.65, 132.40, 131.79, 131.25, 131.13, 131.08, 129.85,
129.52, 128.27, 128.06, 127.24, 126.20, 125.56, 125.51, 124.52,
124.49, 124.33, 120.12, 118.99, 117.93, 107.98, 95.12, 88.31,
71.91, 71.86, 70.66, 70.64, 70.58, 70.55, 70.50, 70.40, 69.80,
69.25, 58.92 ppm; HR-ESI-MS: m/z calcd for C52H62NO13:
908.4221 [M + H]+; found: 908.4053; C52H61NNaO13: 930.4041
[M + Na]+; found: 930.3886.
Fig. 8 Photographs of fluorescent inkjet printing-based paper depicting
fluorescence erasure before and after being exposed to 400 nm LED
under 365 nm irradiation and their rewritable properties.
are denoted in Hz and chemical shifts (d) in ppm. Multiplicities
are denoted as follows: s = singlet, d = doublet, m = multiplet.
High resolution electrospray ionization (HR-ESI) mass spectral
analyses were performed using an AgilentQ-TOF6510. The
UV-visible absorption spectra were recorded using a TU-1901
double beam UV-vis spectrophotometer as powders. The
fluorescence spectra of the samples were measured using a
Hitachi F-7000 fluorescence spectrophotometer using a mono-
chromated Xe lamp as an excitation source. Samples for absorption
and emission measurements were placed in 1 cm  1 cm quartz
cuvettes; all the tests were carried out at room temperature if not
mentioned. Single crystal X-ray crystallographic analyses were per-
formed using a Bruker Xcalibur ECCD system with graphite-
monochromated Mo Ka radiation (l = 0.71073 Å). Cell parameters
were obtained by global refinement of the positions of all collected
reflections. Intensities were corrected for Lorentz and polarization
effects and empirical absorption. The structures were solved by
direct methods and refined by full-matrix least squares on F2.
The X-ray crystallographic files, in CIF format, are available
from the Cambridge Crystallographic Data Centre on quoting
the deposition numbers CCDC 1937449 for 1M.† SEM images
were obtained using an S-4800 (Hitachi Ltd) with an accelerating
voltage of 1.0 kV or 10.0 kV. Samples were prepared by dropping
a dilute solution onto a silicon wafer.
Conclusions
In summary, by rationally introducing multiple intermolecular
noncovalent interactions into a well designed amphiphilic
alkynylpyrene derivative 1, an aggregation-induced photochemical
reaction has been successfully achieved in the system. Treated
under different conditions, such as solvent polarity, concentration,
and ratio of good solvents to poor solvents, the aggregation
behavior of this compound can be fine tuned with emission color
transformation from blue to green. With the formation of highly
ordered aggregates through molecular self-assembly, photo-
dimerization can be realized effectively with 400 nm LED
irradiation. Owing to the invisible and controlled printable
characteristic of the aggregate and the conversion process of
the luminescent materials, we have demonstrated that our
platform can act as a smart luminescent system towards con-
fidential information encryption and decryption with various
General procedure for the synthesis of compounds 1 and 1M
A 100 mL Schlenk flask was charged with 1-bromopyrene, the high-resolution patterns by photolithography and inkjet-
precursors S0 or S1, tetrakis(triphenylphosphine)palladium printing techniques, which protect the recorded confidential
(10 mol%)and cuprous iodide (5 mol%), degassed, and back- information from general decryption methods. Corresponding
filled three times with N2. Diisopropylamine and dried THF to the previous reports,23 the anti-counterfeiting technology
were introduced into the reaction flask using a syringe. The developed here not only possesses highly advanced anti-
reaction was stirred under an inert atmosphere at 70 1C for counterfeit effect but is also user-friendly and convenient to
about 24 h. The solvent was removed by evaporation on a rotary recognize. In addition, the inherent molecular packing of the
evaporator. The residue was purified by column chromatography on materials allows us to quench the luminescence of the as-printed
silica gel (dichloromethane/methanol = 99 : 1) to give 1 or 1M in a characters easily upon visible light irradiation and realize
reasonable yield.
irreversible erasure of the luminescence signal for multiple
Compound 1M. Pale yellow solid. Yield: 72.4%. Rf = 0.51 information rewritable processes. As a result, the present
(dichloromethane/petroleum ether 2 : 1); 1H NMR (DMSO-d6, luminescent materials will provide a platform in the fields of
400 MHz): d = 10.50 (s, 1H), 8.65 (d, J = 12.0 Hz, 1H), optical information storage, information anti-counterfeiting,
8.41–8.32 (m, 4H), 8.28–8.22 (m, 3H), 8.16–8.13 (m, 1H), and erase/rewrite media.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grant No. 21602124), the Natural Science
Foundation of Shandong Province (Grant No. ZR2016BQ11),
and the Young Scholars Program of Shandong University
(2018WLJH40 and 2016TB012).
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