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Highly efficient luminescent benzoylimino
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derivative and fluorescent probe from a
Cite this: Chem. Commun., 2019,
55, 977 photochemical reaction of imidazole as an
Received 25th October 2018,
Accepted 13th December 2018
oxygen sensor†
DOI: 10.1039/c8cc08558g Yue Yu,a Ruiyang Zhao,b Changjiang Zhou,c Xiaoyi Sun,c Shizhao Wang,a Yu Gao,c
Weijun Li, *a Ping Lu, c Bing Yang c and Cheng Zhang *a
rsc.li/chemcomm
A photochemical reaction in which the imidazole ring is opened
under UV irradiation to generate highly luminescent benzoylimino
group by O2 has been discovered. This photochemical reaction
displays great potential for applications that use a fluorescent probe
as a oxygen sensor; it has a lowest detectable volume ratio of B0.2%
and photo storage area.
Imidazole, a classical asymmetric five-member heterocyclic ring,
has been used extensively as a basic structural construction unit
for organic molecular or metal complex1 materials with applica-
tions in photoelectricity,2 catalysis,3 drug synthesis4 and so on.
During recent years, imidazole derivatives were and are also still
increasingly being applied in the photoelectric area, including
OLED,5 non-linear photonics6 etc., owing mainly to the excellent
photoelectric properties of the imidazole structure, such as high
quantum efficiency,7,8 balanced charge mobility9 and so on.
According to current literature, there seemed to be no structural
instability for the imidazole structure, provided that the imidazole
derivatives could display stable luminescence and exhibit good
thermal stability.10 Actually, in the 1960s, Emil H. White11 found
that lophine (2,4,5-triphenylimidazole) would undergo the oxida-
tion reaction via O2 to produce amidine under the strong base
conditions. Some oxidation reactions of the imidazole structure
into amidine by singlet oxygen that was generated from O2 via
energy transfer from the triplet of sensitizers or themselves was
also reported.12 But to the best of our knowledge, there are no
other related reports on the instability of the imidazole structure.
a
State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology,
College of Chemical Engineering, Zhejiang University of Technology,
Hangzhou 310014, P. R. China. E-mail: liwj@zjut.edu.cn, czhang@zjut.edu.cn
b
College of Chemical Engineering, Qingdao University of Science and Technology,
Qingdao, 266042, P. R. China
c
State Key Lab of Supramolecular Structure and Materials, Jilin University,
2699 Qianjin Avenue, Changchun 130012, P. R. China
† Electronic supplementary information (ESI) available: Instrument, synthesis
detail, photophysical, thermal and device data. CCDC 1818464 (DPA-PIM) and
1818466 (DPA-PYZ). For ESI and crystallographic data in CIF or other electronic
format see DOI: 10.1039/c8cc08558g
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Herein, we report a photochemical reaction of the diphenyl-
amine-imidazole structure in which the vinyl bond in the
five-member imidazole ring is opened by O2 to generate a
benzoylimino and benzamide group under UV irradiation. Unlike
previous chemical reactions,11,13 this reaction is a photooxidation
reaction with a rapid reaction rate that does not need any base11
or sensitizers (singlet oxygen),13 which was mainly attributed to
the oxidation by singlet oxygen generated from diphenylamine-
imidazole molecule. Provided that the corresponding product
materials can exhibit excellent luminescent properties, this
photochemical reaction could be effectively employed as an
efficient fluorescent probe as an oxygen sensor with a lowest
detectable oxygen volume ratio of B0.2%, which is among the
best results as compared to most of the oxygen sensors whose
sensitivities ranged from 0.1% to 5%.14a Furthermore, compared
to the lifetime measurement based on the phosphorescence
quenching theory of expensive metal complexes for common
oxygen sensors, this oxygen detector belongs to the fluorescent
probe for oxygen sensor via changing film emission colors
based on cheap organic luminescent molecules. This work will
obviously enrich basic photochemistry reactions, contribute
much to the photoelectronic study of imidazole derivatives,
and bring new material systems for oxygen sensors.14
The photochemical reaction, shown in Fig. 1, that N,N-
diphenyl-4-(1,4,5-triphenyl-1H-imidazol-2-yl) aniline (DPA-PIM)
could directly produce the (z)-N-(benzoylimino)(4-(diphenyl-
amino)phenyl)-N-phenylbenzamide (DPA-PYZ) under UV irradia-
tion (365 nm) and air (O2) conditions. This reaction was first
found during investigations of the photonic properties of DPA-
PIM. It is surprising that the fluorescence color of DPA-PIM’s
film would change rapidly from deep-blue to green under UV
irradiation in air (Fig. 1a), while in the solution case under UV
irradiation, the apparent solution color of DPA-PIM in toluene
changed from colorless to light yellow color together with the
initial blue fluorescence turning to yellow emission (Fig. 1a).
After long-time UV irradiation of the DPA-PIM solution in large
concentration, pure yellow product DPA-PYZ was obtained by
using column chromatography purification. Single crystals of
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Communication
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Fig. 1 (a) Photos under sunlight or UV light of DPA-PIM after UV irradia-
tion exposed to air in film and toluene (10 5 M); (b) the photochemical
reaction of molecular structure from DPA-PIM to DPA-PYZ; single crystal
structures of (c) DPA-PIM and (d) DPA-PYZ.
DPA-PIM and DPA-PYZ were both obtained via the slow diffu-
sion of n-hexane solvent into the chloroform solution, their
crystal structures are shown in Fig. 1c and d, respectively.
Fig. 1c clearly shows the diphenylamine-substituted phenyl-
imidazole structure with a typical five-member imidazole ring
in DPA-PIM. While the measured bond length of 1.27 Å for
CQN and 1.43 Å for C–N effectively confirmed the benzoyl-
imino and benzamide structures in DPA-PYZ (Fig. 1d). The
crystal structures obviously revealed that the vinyl bond in the
five-member imidazole ring of DPA-PIM was opened to form
benzoylimino and benzamide groups in DPA-PYZ during the
photochemical reaction.
In order to further investigate this photochemical reaction,
in situ 1H NMR studies of DPA-PIM in toluene-d8 were per-
formed to trace the reaction process under different UV irradia-
tion time, with that DPA-PYZ used as a reference (Fig. 2a). DPA-
PIM exhibited the obvious character signals with a doublet
peak at 7.54 ppm and a triplet peak at 7.22 ppm, while DPA-PYZ
displayed much more character signals with a triplet peak at
6.65 ppm, a multiplet peak at 7.90 ppm and three doublet
peaks at 7.62 ppm, 7.22 ppm, and 6.75 ppm, respectively. When
the UV irradiation time was prolonged from 0 min to 45 min,
the intensity of signals that correspond to DPA-PIM gradually
decreased and those signals that correspond to DPA-PYZ were
simultaneously enhanced in peak intensity. After UV irradia-
tion for 90 min, the signal at B7.22 ppm gradually changed
from the initial triplet peak to a doublet peak, and the resultant
1
H NMR spectra came to be nearly the same as that of DPA-PYZ.
There were no other signals in the 1H NMR spectra except for
the signal peaks of DPA-PIM and DPA-PYZ during the entire
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Fig. 2 (a) The in situ 1H NMR spectra of DPA-PIM in toluene-d8 solvents
under UV irradiation for different time with that of DPA-PYZ used as a
reference. (b) In situ absorption spectra of DPA-PIM in toluene solvent at
10 5 mol L 1 under different UV irradiation (365 nm, 6 w) time in air (O2)
with that of DPA-PYZ used as a reference.
photooxidation reaction process. All of these changes in the
NMR spectra demonstrated that DPA-PIM transformed directly
to DPA-PYZ gradually with increasing UV irradiation time, and
DPA-PYZ was the sole product without any other by-products in
this photo-oxidation reaction.
The in situ UV absorption spectra of DPA-PIM under UV
irradiation were also studied to further monitor the photo-
chemical reaction (Fig. 2b). DPA-PIM exhibited an obvious
strong absorption peak around 350 nm, while DPA-PYZ dis-
played a relatively red-shifted strong absorption peak range
around 375 nm. When the irradiation time increased, the peak
intensity of DPA-PIM UV spectra gradually decreased, and at the
same time, a new peak at about 375 nm that corresponds to
that of DPA-PYZ began to appear and gradually increased.
There were no other special peaks except for those of DPA-
PIM and DPA-PYZ in the UV spectra during the UV irradiation
process. These results further demonstrated that DPA-PIM was
exclusively transformed to DPA-PYZ in the photochemical reac-
tion, consistent with the experimental results of previous in situ
1
H NMR spectra (Fig. 2a). In order to explore the conditions
of this photooxidation reaction, two groups of UV spectra were
measured as the control experimental data (Fig. S1, ESI†).
When DPA-PIM solution was kept in darkness without UV light
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exposure (Fig. S1a, ESI†) or sealed in N2 without exposure to O2

(Fig. S1b, ESI†), no new peaks emerged in either of their UV
spectra at B375 nm that corresponds to DPA-PYZ. Thus UV
irradiation and O2 are presumed to be two necessary reaction
conditions. In addition, the higher UV irradiation intensity
could accelerate the photochemical reaction, which could be
concluded from the gradually increasing peak at B375 nm in
Fig. S2 (ESI†), which indicates that UV intensity had a positive
correlation with the photochemical reaction rate.
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The electron spin-resonance spectroscopy (ESR) data showed

signals15 of singlet oxygen15a and superoxide anion15b,c radical
in the observed oxidation reaction (Fig. S3a and b, ESI†). In
order to figure out which reactive oxygen was the oxidant for
this oxidation reaction, the control experiment was carried out.
When triethylenediamine (DABCO), the efficient singlet oxygen
quencher,16 was added into the DPA-PIM solution, a significant
decrease of the reaction rate was observed (Fig. S4a and c, ESI†),
which indicates that singlet oxygen played a key role in the
photochemical oxidation reaction of DPA-PIM. After the addi-
tion of trapping agent benzoquinone (BQ) for superoxide anion
radical,16 such results were not observed (Fig. S4a and b, ESI†).
Considering the ESR signal of the superoxide anion radical, the
influence of the superoxide anion radical for the observed
photochemical oxidation reaction was unclear, and it might
be generated by the electron transfer from diphenylamine-
imidazole molecule to singlet oxygen. The above experiments
proved that the observed photochemical oxidation reaction of
DPA-PIM might be mainly attributed to the oxidation of singlet
molecular oxygen. Further research on the mechanism of this
photochemical reaction is undergoing.
Surprisingly the product DPA-PYZ of this photochemical
reaction showed excellent luminescent properties. DPA-PYZ
was measured to be of a strong yellow emission with lmax at
552 nm (Fig. S5, ESI†) as well as a high fluorescent quantum
yield of B55% through an integrating sphere photometer in
spin-coated film. Lifetime measurement showed the fluores-
cence nature (t = B4.8 ns) of DPA-PYZ (Fig. S6, ESI†), not the
thermally activated delayed fluorescence17 or room-temperature
phosphorescence18 (the phosphorescence was obtained around
650 nm with t = B3.1 ms under 77 K). Theoretical electronic
cloud distribution predicted that the HOMO was mainly located
at the triphenylamine moiety, while the LUMO was mainly
dominated by the newly-generated benzoylimino part (Fig. 3a,
please see Tables S1 and S2 in ESI† for details). When DPA-PYZ
was dissolved in THF solvents, it displayed a weak orange
emission with lmax at 580 nm. When the water proportion
reached 90% in a THF/water mixture, the PL intensity of DPA-
PYZ reached the maximum level (Fig. 3b), which effectively
demonstrated the aggregation-induced emission (AIE)19 property
of DPA-PYZ. Crystal structures showed that the benzoylimino-
benzamide part in the DPA-PYZ molecule was quite torsional and
nonplanar, and there were many intermolecular CH–p inter-
actions (Fig. S7, ESI†), which enabled the observed AIE effect of
DPA-PYZ. Interesting was that the DPA-PYZ crystal exhibited a
blue emission with lmax at 458 nm different from its spin-coated
film (Fig. S5, ESI†), possibly due to the restriction of the
Fig. 3 (a) Optimized molecular geometries and calculated spatial distri-
butions of HOMO and LUMO of DPA-PYZ; (b) fluorescence spectra of
DPA-PYZ in the THF/water mixtures with different fractions of water (10 5 M);
(c) photos under UV light (365 nm, 24 W) in glove box of spin-coated DPA-
PIM film before and after photo-patterning via UV light for 30 seconds
through a black paper with patterned cavity of ‘‘ZJUT‘‘.
intramolecular rotation effect.19,20 Compared to the DPA-PIM,
the photo-oxidation product DPA-PYZ exhibited a relatively
weaker thermal property with a Td of 250 1C (weight loss: 95%)
as shown in Fig. S8 (ESI†). Thus DPA-PYZ was fabricated by spin-
coated method as emitter layer to obtain the electroluminescent
device with a maximum luminous efficiency of 1.76 cd A 1 and a
maximum brightness of 2388 cd m 2 (Fig. S9, ESI†). Thus,
benzoylimino moiety might be a promising structure unit for
high-performance photoelectronic materials.
Given the high fluorescent quantum efficiency in DPA-PYZ’s
aggregated state as well as the Förster resonance energy trans-
fer due to the effective overlap between DPA-PYZ’s absorption
(Fig. 2b) and DPA-PIM’s PL spectra (Fig. 4), short-time irradia-
tion (30 s) of DPA-PIM film under UV light (365 nm, 6 W) in air
could rapidly produce the strong yellow emission deriving from
DPA-PYZ. This enabled us to easily obtain the photo-patterned
film by controlling the position/area exposed to UV light
(Fig. 3c), and the obtained photo-patterned film was kept stable
under a lack of O2, which should be applied in the photo
storage areas. Moreover, the PL spectra of DPA-PIM film in the
gas mixture of N2 and O2 with different volume ratio were also
investigated to roughly evaluate the oxygen sensitivity (Fig. 4).
The DPA-PIM film displayed totally different PL spectra in
different O2 concentrations. As the O2 volume ratio increased,
the PL peak around 520 nm, corresponding to the emission
of DPA-PYZ, rose gradually as PL intensities became larger.

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Fig. 4 The normalized PL spectra of DPA-PIM film in the gas mixture of
N2 and O2 (different volume ratio) measured by the Fluorolog-3 (HORIBA)
instrument with the same operating parameter (wavelength range, scan
rate, slit width etc.).
When the O2 volume ratio was as low as 0.2%, a slight change
in the PL spectra of the DPA-PIM film was still observed around
B450–550 nm in comparison to that in pure N2, which
indicates the existence of a PL peak that corresponds to the
emission of DPA-PYZ. Thus, it was obvious that the photo-
chemical reaction from DPA-PIM to DPA-PYZ could be employed
as an efficient fluorescent probe by changing the film emission
color for an oxygen sensor. Its lowest detectable oxygen volume
ratio was as low as B0.2%, among the best results as compared
to most of the oxygen sensors whose sensitivities ranged from
0.1% to 5% based on phosphorescence quenching theory.14a
As for other reactions used for oxygen sensors, in current
reports,14b–d they focused on the detection of active oxygen
such as singlet oxygen in the cell, but not ground state oxygen.
Provided the very small DPA-PYZ molecule (o1%, no corres-
ponding signals in NMR spectra) generated in the DPA-PIM
film during the PL measurement process, the efficient fluo-
rescent probe for oxygen sensor should be mainly attributed to
the effective Förster resonance energy transfer from DPA-PIM to
DPA-PYZ. These results indicated that this photochemical
reaction might bring great potential applications in photo-
storage, fluorescent probe as an oxygen sensor or other related
photoelectric areas.
In summary, a photochemical reaction of the five-member
imidazole ring with the participation of singlet oxygen was
discovered in which the benzoylimino derivative was confirmed
to be the sole reaction product from the single crystal structures
and in situ NMR spectra. UV irradiation and O2 were proved to
be the two essential conditions for this photochemical reaction.
Surprisingly, the photochemical reaction product DPA-PYZ
exhibited excellent luminescent properties with a high fluo-
rescent efficiency in solid state as well as the AIE effect. Photo-
chemical reaction could be employed as an efficient fluorescent
probe as an oxygen sensor with a lowest detectable oxygen volume
ratio of B0.2%, which should be mainly attributed to the effective
Förster resonance energy transfer effect. Compared to the lifetime
980 | Chem. Commun., 2019, 55, 977--980
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measurement based on phosphorescence quenching theory of
expensive metal complex in the common oxygen sensors, this
oxygen detector belongs to the fluorescent probe for oxygen sensor
via changing film emission colors based on cheap organic lumi-
nescent molecules. This work will enrich the basic photochemistry
reaction, contribute much to the photoelectronic study of imida-
zole derivatives and bring new material systems for oxygen sensor.
Thanks to financial supports from National Natural Science
Foundation of China (51603185 and 51673174) and Zhejiang
Provincial Natural Science Foundation of China (LZ17E030001).
Conflicts of interest
There are no conflicts to declare.
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