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Materials Chemistry C
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Non-invasive fluorescence switch in polymer films

based on spiropyran-photoacid modified TPE†
Cite this: J. Mater. Chem. C, 2018,
6, 2113
Qi Yu,a Xing Su,a Ting Zhang,b Yu-Mo Zhang,a Minjie Li, b
Yifei Liu *a and
Sean Xiao-An Zhangb

Received 10th November 2017,
Accepted 25th January 2018
DOI: 10.1039/c7tc05142e
rsc.li/materials-c
Non-invasive fluorescent molecular switch is very challenging to achieve in solid state. Here, a new
multi-stimulus-responsive fluorescent molecular switch of SPPATPE was prepared by linking spiropyran-
photoacid (SPPA) with tetraphenylethene (TPE). The isomerization of SPPATPE can be triggered with
either visible light/dark or acid/base in solution. Both ring-closed form (RCF) and ring-open form (ROF)
of SPPATPE exhibit aggregation-induced emission (AIE). The RCF SPPATPE aggregates give out a cyan
emission, which is assigned as the local excited emission of TPE moiety, while ROF SPPATPE have two
forms of aggregation states, which give out two red emissions from intramolecular charge transfer. By
selecting a suitable polymer of polyvinyl pyrrolidone (PVP) as the matrix, which gives the molecules a
moderate alkaline environment, SPPATPE can exhibit non-invasive light/heat responsive emission switch
in the polymer thin film with both good waterproofness and good processibility, which makes this kind
of hybrid material potentially applicable in photo sensing, rewritable display, etc.

1. Introduction responsiveness in solid state because of the large change of

Fluorescent molecular switches1–4 (FMSs) have been extensively
explored recently because of their stimulus-responsive emissions
and a broad range of applications in optical data recording,5,6
chemical sensors,7–9 displays10,11 and bio-imaging.12–14 FMSs
that respond to a diverse range of triggers, such as UV/vis
light,15,16 heat,17,18 mechanical/hydrostatic force,19,20 acid/
base,21 and chemical vapour,22 have been achieved. So far,
great progress has been achieved in improving the properties
of FMSs, such as the number of states,23 color contrast,24,25
on/off ratio,26 sensitivity and reversibility,27–29 to pave way for
their practical application. Among these studies, non-invasive
stimulus responsiveness in solid state is very important for
their practical application in certain areas such as storage or
display,30 because it is easily accessible and does not generate
by-products. It has been known that some molecular switches
(such as azo-benzene and diarylethene) can respond to light or
heat in solid state; however, the color contrast in these FMSs is
usually low.31–33 In contrast, FMSs that apply molecular switches
such as spiropyran and benzoxazine can lead to high-contrast
colors, whereas, it is hard to achieve their non-invasive stimulus
a
College of Chemistry, Jilin University, Changchun, 130012, P. R. China.
E-mail: liuyifei@jlu.edu.cn
b
State Key Lab of Supramolecular Structure and Materials, College of Chemistry,
Jilin University, Changchun 130012, China
† Electronic supplementary information (ESI) available. CCDC 1571191. For ESI
and crystallographic data in CIF or other electronic format see DOI: 10.1039/
c7tc05142e
molecular polarity and conformations during the tautomeriza-
tion;34,35 therefore, strategies that can realize solid-state color
switching in spiropyran (or benzoxazine)-based FMSs are highly
needed.
In our previous work, we have developed several TPE
integrated molecular switches (spiropyran, benzoxazine) and
achieved high-contrast multi-color states by cooperative mod-
ulation of both molecular structure and the molecular packing
modes.36–38 However, the stimuli mainly include grinding/
solvent and acid/base, which are invasive, and byproducts
(like salt) might be introduced into the system. Here, we focus
on achieving non-invasive stimulus responsiveness in solid state.
It has been proposed that it is the large change in size/geometry
of spiro compounds that prevents their switching in solid state,
so bulky substituents (such as adamantane) are used to enable
the switching in crystal.39 Meanwhile, some studies report that it
is not because of the change in geometry/size but the generation
of high-energy phenolate anion species that cause a very fast
ring-closing reaction,40,41 and high electron-withdrawing sub-
stituents nearing the highly reactive anion, such as nitro and
quaternary amines, as well as low temperature are used to
achieve light responsiveness in crystals.42–44 However, the high
electron-withdrawing substituents usually cause the quenching
of emission, and low-temperature is not feasible for practical
applications either.45
In this paper, we want to use protons to stabilize the
phenolate anion of spiropyran and avoid the quenching of
emission to achieve solid state fluorescence switching. External

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protons can inevitably leak from the system, so the protons

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should be tagged to spiropyran molecules. A spiropyran-based

photoacid can achieve such a goal.46,47 Different from the
phenolic moiety as the photoacidic structure, which bears the
mechanism of excited state photon transfer (ESPT) and exhibits
an extremely short lifetime,48,49 the ‘‘photoacid’’ used here is
based on a different mechanism of photo-induced molecular
tautomerization and proton dissociation and behaves more like
a steady state photoacid because of the long lifetime. So, here a
new FMS is designed by integrating a spiropyran-based photo- Fig. 1 (A) Structural formula of SPPATPE and (B) its corresponding single-
crystal structure; (C) the 1H-NMR spectrum in DMSO.
acid with TPE (denoted as SPPATPE). After tagging the acidic
group, the spiropyran species exist in its ring-open form with-
out any external stimuli. The new FMS not only preserves the during crystallization.37 Here, crystals were cultured in chloro-
isomerization property under visible light/dark and acid/base form and ethanol, and the single-crystal XRD proved that the
stimuli in solution, but also show high contrast emission ROF was preserved in the crystals (CCDC: 1571191). This
between its ring-closed and ring-open aggregation states. More- was because (i) –SO3H had strong acidity (pKa = 1.3)50 and
over, in a proper polymer matrix, such as PVP, which provides a (ii) –SO3H was chemically linked to the molecules and cannot
moderately alkaline environment, red/cyan emission switching be expelled from the crystals during crystallization.
upon non-invasive stimuli of light and heat was achieved
eventually with high reversibility. To explore the possibility 2.2. Multi-stimulus-responsive properties of SPPATPE in
for practical application, SPPATPE/PVP/PDMS hybrid material solution
with both waterproofness and good processibility into nano-
fibers by electrospinning have been prepared, and the applica- First of all, we studied the tautomerization properties of
tions in photo-sensing and rewritable displays have been SPPATPE in solution; two pairs of stimuli of base/acid and
demonstrated. visible light/dark were used to trigger the ROF/RCF transition.
SPPATPE in ethanol had two absorption peaks at 390 nm
and 483 nm, respectively, which were assigned to its open form.
2. Results and discussion When a base was added, these two peaks gradually decreased
2.1. Synthesis and characterization of SPPATPE with increasing amount of base. Take NaOH as the base for
example, these two absorption peaks vanished when 0.9 equi-
SPPATPE was synthesized by a four-step reaction (Scheme 1).
valent of NaOH was added, indicating all molecules in ROF
SPPATPE is soluble in common organic solvents, such as
changed to RCF eventually (Fig. 2A). The ROF to RCF transition
chloroform, methanol, ethanol and DMSO. Fig. 1 shows the
1 could be identified by 1H-NMR (Fig. S1, ESI†). Furthermore, one
H-NMR spectrum of SPPATPE in DMSO; the single peak of
thing that should be pointed out is that the absorption spectra
–CH3 on indole indicates that the product in DMSO exists in its
of Fig. 2A were taken after the solution was equilibrated for at
ROF. In our previous work, ROF of protonated spiropyran-TPE
under acidic conditions (40 equivalent) can undergo the ROF to
RCF transition during crystallization by releasing a proton.
Only when the excess acid was added, ROF can be preserved

Fig. 2 UV-vis absorption spectra of SPPATPE in ethanol solution (5  10 5 M)

(A) after addition of different equivalents of NaOH and maintained for one
minute; (B) after treated with 0.9 equivalent of NaOH then treated with
different equivalents of HCl; (C) irradiated with 483 nm light for different
times and placed in the dark for 5 hours; (D) irradiated with 390 nm light for
Scheme 1 Synthetic routes for SPPATPE. different times.

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least one minute. If the spectra were taken immediately after
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the alkali was added, an absorption peak at 623 nm appeared,
which was assigned to the absorption of deprotonated pheno-
late form of ROF and the color of the solution was cyan at that
time, which turned to pale yellow very quickly, indicating that
the ring-closing process was completed (Fig. S2, ESI†). How-
ever, one question arose that why 0.9 equivalent of NaOH could
result in the complete conversion from ROF to RCF. It could be
attributed to the existence of a pre-equilibrium of ROF and RCF
in the ethanol solution. Since the solution of SPPATPE was
stored in a brown volumetric flask capped with tinfoil to avoid
the influence of light before testing, the visible light induced
structure conversion could be ruled out. When excessive,
100 equivalent, of HCl was added to SPPATPE in ethanol, the
absorption peaks at 390 nm and 483 nm enhanced gradually
with time and did not change obviously when the solution was
stored for as long as 6 hours, and all SPPATPE was believed to
be in ROF (Fig. S3, ESI†). By calculation, it was found there 22%
RCF species co-existed with ROF in the solution. This isomer-
isation process triggered by acid/base was reversible. Upon
addition of HCl into the above SPPATPE solution treated with
0.9 equivalent of NaOH, the absorption peaks at 390 nm and
483 nm appeared gradually, and they reached their original
level when 100 equivalent of HCl was added after equilibrium
for 2 hours (Fig. 2B). The excess acid required to complete the
RCF to ROF transition indicated the energy barrier from RCF to
ROF was much higher than that from ROF to RCF transition.
Actually, the pre-equilibrium between ROF and RCF in solution
was concentration-related, the lower the concentration of
SPPATPE, the more the containment of the RCF species; the
containment of the RCF species increased from 40% to 74% as
the concentration decreased from 2  10 5 M to 1  10 5 M
(Fig. S4a, ESI†), whereas the containment was 0% by calcula-
tion when the concentration was larger than 1  10 4 M.
Similar results could be observed even when the protic solvent
of ethanol was changed to aprotic DMSO (Fig. S4b, ESI†). This
also explained why only ROF was observed in DMSO in 1H-NMR
when the concentration of SPPATPE was in the 10 3 M scale.
Moreover, in order to verify whether the pre-equilibrium
between ROF and RCF is just a result of autoprotolysis in the
solvent, we measured the equilibrium constants and the
kinetics at different SPPATPE concentrations. Detailed experi-
mental process and data are given in the ESI† (Fig. S5–S7). The
results show the equilibrium constants varied with concen-
tration and the concentration dependence was a complicated
equilibrium process of dissolution, dissociation and isomeriza-
tion and not just a result of autoprotolysis.
Besides the base/acid sensitivity, the light sensitivity was
also studied. Because SPPATPE in ROF showed two absorption
peaks at 483 nm and 390 nm in ethanol solution, we studied
the photo isomerization properties with both wavelengths with
the lamp of a spectrofluorometer (RF-5301PC) as the light
resource. The cuvette was placed on the sample holder and
the excitation slit width was set as 20 nm and the excitation
wavelength was set to 483 nm and 390 nm. The optical power
densities were measured to be 5.6 mW cm 2 and 2.1 mW cm 2
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using an optical power density meter. After the sample was
irradiated for a certain time, the cuvette was transferred to an
adjacent UV-vis spectrophotometer quickly and the absorption
spectrum was recorded. When illuminated with 483 nm light,
the intensity of the two absorption peaks of ROF in ethanol
solution decreased gradually with time, which indicated the
structural change from ROF to RCF. After 60 minute irradia-
tion, the shape of the curve did not change anymore although
the absorption peak did not decline to zero. This indicated
equilibrium of ROF and RCF was achieved, and ROF could not
switch to RCF completely upon this power light irradiation.
Then the solution was placed in the dark for 5 hours, and most
of RCF changed back to ROF again (Fig. 2C). When 390 nm was
used to irradiate the sample, the same phenomenon was
observed. However, the transition ratio was lower (Fig. 2D
and Fig. S8, ESI†). Moreover, the photo isomerization quantum
yields were calculated to be 0.003 and 0.013 for the first minute
of irradiation with 483 nm and 390 nm, respectively (detailed
information can be found in ESI†).
2.3. Aggregation-induced emission (AIE) properties and
fluorescence mechanism of ROF and RCF of SPPATPE
Because of the free rotation of the benzene groups in TPE, the
emission of SPPATPE in ROF and RCF were both very weak in
solution. Different solvent systems were used to study the AIE
performance of the two forms of SPPATPE. When a poor solvent
of hexane was added to the RCF SPPATPE THF solution, the
absorption peak gradually decreased with hexane fractions
because aggregates formed (Fig. 3A). A cyan emission centered
at 480 nm appeared when the hexane proportion reached 80%,
and the emission of the aggregates could be easily observed by
naked eye at a hexane proportion of 90% (Fig. 3B). For ROF
SPPATPE, because of the high polarity of the molecule, ethanol
was a better solvent than THF and was used in the AIE perfor-
mance test. An emission peak centered at about 650 nm appeared
Fig. 3 (A) UV-vis absorption spectra and (B) PL spectra of ring-closed
SPPATPE (5  10 5 M) in different THF/hexane (v/v) mixtures; (C) UV-vis
absorption spectra and (D) PL spectra of ring-open SPPATPE (5  10 5 M)
in different ethanol/hexane (v/v) mixtures. Inset: Corresponding fluores-
cent images taken under UV light (365 nm).
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Fig. 4 Molecular orbital of HOMOs and LUMOs of RCF (left) and ROF
SPPATPE (right) calculated using B3LYP/6-31G(d) by Gaussian 09.
and its intensity increased gradually with hexane fraction, while
the absorption peaks showed no obvious changes (Fig. 3C and D).
Interestingly, the emission peak of the aggregates at 90% hexane
fraction blue shifted gradually to 580 nm after 8 minutes (Fig. S9,
ESI†) while the absorption peaks still showed no obvious changes.
More interestingly, when the original good solvent was changed to
DCM, the emission shifted to the opposite direction. The main
emission peak was located at about 580 nm when hexane fraction
was in the range of 30% to 80%, but it changed to 650 nm when
the hexane fraction increased to 90% (Fig. S10, ESI†). This might
have resulted from the different aggregation states in different
solvent environments. Therefore, PXRD was performed to deter-
mine these aggregation states. The sample aggregated in ethanol/
hexane with emission at 650 nm was not observed because of its
rapid transition to the state with emission at 580 nm, while the
relatively stable aggregates with 580 nm emission was obtained,
and they were crystalline. In the DCM/hexane system, the sample
with emission at 580 nm obtained from 60% poor solvent fraction
was confirmed to be crystalline, while sample with emission at
650 nm obtained from 90% poor solvent fraction was confirmed
to be amorphous (Fig. S11, ESI†). Thus, both RCF and ROF
SPPATPE exhibited aggregation-induced emission properties.
RCF aggregates emitted cyan emission at 480 nm, while ROF
aggregates emitted different emissions at 580 nm and 650 nm
from different aggregation states.
Further, theoretical calculations were performed to disclose
the origin of the cyan and red emissions (Fig. 4). For RCF
SPPATPE, the electron density of HOMO and LUMO were
mainly distributed on TPE the moiety; this indicated that the
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Fig. 5 (A) Reversible switch between ROF SPPATPE powder crystals (red)
and RCF SPPATPE powders (cyan) under ammonia fuming and 135 1C
treatment; photos were taken under 365 nm light. (B) PL spectra of pristine
ROF SPPATPE powder crystals (black line); RCF SPPATPE powders derived
from triethylamine fuming (cyan line) and ammonia fuming (red line); and
ROF SPPATPE recovered from 135 1C heat annealing of the ammonia
fumed sample (blue line).
cyan emission should be assigned as a localized excited (LE)
emission of TPE. For ROF SPPATPE, the electron density of
HOMO was distributed on the TPE moiety, while the electron
density of LUMO was distributed on the indolium moiety,
suggesting that the red emission originated from the intra-
molecular charge transfer (ICT). These results were consistent
with our previous results on other types of molecular switch-
modified TPE systems.36–38
2.4. Structural transition properties in solid state
The above study has shown that SPPATPE can reversibly switch
between ROF and RCF in solution, and ROF and RCF showed
distinctive emissions in their aggregation states. Here we study
whether these switching processes as well as the emission
change can be realized in solid state. First of all, acid/base
was utilized to trigger the isomerisation. Crystalline ROF
SPPATPE cultured from chloroform/methanol was used as the
initial state. When fumed with the alkali vapor of triethylamine
and ammonia, RCF SPPATPE was obtained with emission
switching from 630 nm to 480 nm. The sample derived from
triethylamine fuming could maintain its stable state not only at
room temperature but also at 200 1C for one hour, while the
emission of the ammonia fumed sample could shift to 630 nm
again upon heating at 135 1C (Fig. 5). This could be because
of the easier volatilization of ammonia. Besides acid/base and
UV/visible light were also used to (induce the structure conver-
sion) trigger the isomerization. First, blue light (449 nm, 20 W)
was utilized to irradiate the crystals of ROF SPPATPE from
5 minutes to 60 minutes; however, no response occurred.
Considering that the weak interactions between the molecules
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Journal of Materials Chemistry C
in the crystal may block the proton transfer as well as the
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structural conversion, we converted SPPATPE ROF crystalline
state into amorphous state through grinding.51,52 However,
light still could not trigger the isomerization even after 30
minutes of irradiation. The main reason that SPPATPE could
not realize tautomerization through visible light irradiation in
solid state was that the pKa of sulfonic acid was much greater
than that of phenol hydroxyl,50,53 which means that there was
no receptor to stabilize the proton; even if the ring close process
occurred, the proton would turn to combine with the phenol
oxygen, leading to the ring-open reaction again.
2.5. Non-invasive fluorescence switching in polymer films and
fibers: preparation and performance optimization
We proposed that the strong acidity of sulfonic acid prevented
the ROF to RCF transition in solid state upon light irradiation.
In order to stabilize the protons and avoid their attack on the
spiro C–O bond, PVP, an alkaline polymer, was selected as
the temporary proton container. SPPATPE could Successfully
convert its structure from ROF to RCF through blue light
(449 nm, 20 W the optical power density was 26.8 mW cm 2
when the irradiation distance was one centimeter) irradiation
when incorporated into the PVP film along with emission
switching from the original dark orange-red to bright blue.
However, the reverse process could not be realized through UV
light (254 nm, 6 W) irradiation; this means higher power was
needed to overcome the energy barrier to release protons and
break the spiro C–O band. As expected, when the blue emission
film was heated at 130 1C for a few seconds, the emission turned
to bright orange-red again (Fig. 6A and B). This reversible
process with non-invasive stimuli of light and heat could be
repeated many times without emission peak shift and intensity
declination (Fig. 6C).
The absorption and PL spectra of the pure PVP film were
measured and compared with the SPPATPE doped PVP film. It
showed that PVP itself had no effect on the absorption and
emission properties of the SPPATPE doped film (Fig. S12, ESI†).
In order to confirm the necessity of PVP, the control polymer of
neutral PMMA was used as the matrix. Results indicate that the
Fig. 6 (A) Fluorescence switch of SPPATPE/PVP film with blue light
(449 nm) and heat (130 1C) annealing sequentially; (B) their corresponding
PL spectra; (C) wavelength contrast profiles of the film with switching
cycles.
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ROF SPPATPE incorporated PMMA film could not convert its
orange-red emission to blue emission upon blue light irradia-
tion. RCF SPPATPE incorporated PMMA film could not change
its emission upon heating either (Fig. S13, ESI†). This indicated
that the alkaline environment of PVP played an important role
in the controllable structural change between ROF and RCF
SPPATPE. In order to further confirm whether the combination
of SPPATPE with PVP was essential for the light/heat triggered
emission switching system, the control molecule of SPTPE in its
protonated ring-open form (treated with hydrochloric acid),
which had similar structure than SPPATPE but had no alkyl
sulfonate, was incorporated into PMMA and PVP and subjected
to light irradiation and heat treatment. However, although the
ROF of SPTPE could convert to RCF upon visible light irradia-
tion, the reverse process could not be realized either by UV light
(254 nm, 6 W) irradiation or by heat treatment (Fig. S14, ESI†).
This indicated that ROF of SPTPE could not realize the non-
invasive stimulus-induced fluorescence switching even in the
PVP environment because of proton diffusion and was trapped
into the polymer matrix and could not be withdrawn back to
the molecule due to the lack of chemical bonding compared
with that in SPPATPE.
After confirming the necessity of photoacid modification
and the selection of PVP for the non-invasive fluorescent
switching, we turned our attention to the detailed formulation
of the hybrid film. Firstly, PVP with different molecular weights
of 40 000 (40 K), 360 000 (360 K) and 1 300 000 (1300 K) were
used as the matrix. The hybrid films had the same weight
content of SPPATPE (5 wt%) and were subjected to the same
blue light irradiation (Fig. S15a, ESI†). The PL spectra of the
three films were recorded under the same irradiation time
(Fig. S15b–d, ESI†). After comparing the ROF to RCF conversion
efficiency, we noticed that the conversion completed after
30 min irradiation when 40 K PVP was used as the matrix,
while the other two films did not convert sufficiently. It was
reasonable to assume that the conformational change would
require a certain excess free volume around the functional
molecule in the matrix. So, this indicated that the free volume
of the polymer matrix was also important for the tautomeriza-
tion. As the molecular weight of the polymer increased, the
glass transition temperature was higher and the free volume
decreases.54,55 Therefore, 40 K PVP was an ideal matrix for the
fluorescence switching film.
Since PVP is a water-soluble polymer, environmental humidity
would affect the stability of the film. From the application point of
view, PDMS as a copolymer was blended to enhance the humidity
resistance of the film. 90% PDMS containment improved the
waterproofness significantly. The hybrid film was maintained
perfectly after dipping in water for 60 minutes, and the heat
induced emission change had no affect (Fig. S16a, ESI†). Also, the
SPPATPE doped PVP film without PDMS blending dissolved in
water very quickly (Fig. S16b, ESI†). Then, PVP/PDMS films with
different weight contents of SPPATPE were prepared and the
stimuli responsive emission switching property was investigated.
The hybrid film with 0.2% weight content of SPPATPE had a
shorter response time from ROF to RCF (the time constant was
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calculated to be 3.1 min); however, the emission intensity was
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relatively weak, and the color contrast was not clear either
(Fig. S17, ESI†). The hybrid film with 0.3% weight content of
SPPATPE had higher intensity and color contrast of emission.
Meanwhile, the response time became longer (Fig. S18, ESI†). The
time constant was calculated to be 17.6 min. In contrast, the
hybrid film with 0.22% weight content of SPPATPE had moderate
Fig. 7 (A) Images of SPPATPE/PVP/PDMS (0.22% weight content) film
after irradiation for different times with blue light (449 nm) irradiation,
taken under ambient light (up), under UV light (down, ex = 365 nm);
(B) their corresponding PL spectra and (C) CIE graph.
Fig. 8 Photoluminescence images (up, ex = 365 nm) and corresponding
PL spectra (down, ex = 400 nm) of SPPATPE/PVP/PDMS (0.22% weight
content) film after irradiation for different times with a solar simulator.
Fig. 9 Illustration on the rewritable display with the SPPATPE/PVP/PDMS hybrid film using blue light and heat as the writing and erasing stimuli
sequentially. The size of the film was 2 cm  2 cm and the photos were taken under 365 nm irradiation.
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response time and color contrast visible to the naked eye (Fig. 7).
The time constant was calculated to be 15.7 min in the process of
ROF to RCF conversion. The fluorescent quantum yield of the
hybrid film before blue light irradiation was 13.72%, and it
changed to 13.50% after the emission changed to blue. Then
the film was subjected to 130 1C heat treatment for several
minutes and the emission changed back to orange-red. Several
cycles of blue light/heat treatment were performed, and the
emission peaks as well corresponding intensity of the film showed
no obvious changes (Fig. S19, ESI†).
Moreover, this kind of hybrid polymer showed good proces-
sibility and could be processed using electrospinning to con-
struct nanofibers, and the non-invasive fluorescence switching
property was well preserved (Fig. S20, ESI†). SPPATPE was well
dispersed in the fibers, and the entire long fiber exhibited
uniform emission before and after the light or heat treatment.
2.6. Application demonstration as photo sensor and
rewritable display
As we know that protection from sunlight is highly needed
when people stockpile some medicament or chemicals,
because some of them would deteriorate and lose their original
function under light irradiation. Thus, a photo sensor that can
record whether they have been exposed to sunlight is in great
need. Traditional photochromic materials can respond to light,
but they recover the color in dark, which is not suitable for such
applications. First, we test whether sunlight can trigger the
emission change and preserve the color in the dark. Here, a
solar simulator was used to irradiate the hybrid film (0.22%
weight content of SPPATPE/PVP/PDMS), and the PL spectra as
well as the corresponding photo images both confirmed that
the emission changed from red to blue with time (Fig. 8), and
no obvious color changes were observed when the film was
placed in the dark for 20 days (Fig. S21, ESI†). Only when the
film was subjected to heating could it change back to red
emission. This indicated that the hybrid film could be used
to record the history of light irradiation. In this way, one could
estimate the usability of the medicament or chemicals through
observation of the color or emission change of the hybrid film
that was put together with them without using expensive
special tests.
Furthermore, this hybrid polymer film could also be used in
the field of rewritable displays because of controllable and
reversible emissions. Both light and heat could be used as
writing or erasing methods, as shown in Fig. 9. Using a photo
mask, a pattern could be copied on the film through blue light
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irradiation with ROF as the initial state; the pattern emitted a
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cyan emission, while the background exhibited an orange-red
emission under UV light (365 nm). When the photo mask was
removed, the ROF converted to RCF upon further irradiation,
and the whole film emitted a cyan emission. When a heated
mould was stamped on the film, the image of the embossment
could be transferred on it. Further heating of the whole film
could make it back to the initial state.
3. Conclusions
A new fluorescent molecular switch of spiropyran-photoacid
modified TPE was synthesized. Its tautomerization between
ROF and RCF was achieved in solution by visible light/dark as
well as acid/base stimuli. Due to the AIE effect, both ROF and
RCF did not show emission in solution, but showed strong
emissions in aggregation states. Moreover, non-invasive stimu-
lus (light/heat)-triggered reversible tautomerization in the solid
matrix of the PVP polymer could be achieved. Incorporation of
another polymer of PDMS could greatly improve the water-
proofness of SPPATPE/PVP, and SPPATPE/PVP/PDMS nano-
fibers were also prepared by electrospinning to demonstrate
the processibility of the composite materials. The non-invasive
stimulus-triggered controllable emission switching in solid
state enabled this kind of fluorescent molecular switch for
practical applications in the field of sensing and rewritable
displays. We will continue our efforts for performance optimiza-
tion (e.g. responsive time improvement) by molecular structural
design in the future work.
4. Experimental section
4.1. Materials
Iodomethane, n-butyl lithium, bis(pinacolato)diboron, Pd(Ph3P)4,
diphenylmethane, 4-bromobenzophenone, tosilate, 4-bromophenyl-
hydrazine hydrochloride, 3-methyl-2-butanone, PVP, and
1,2-oxathiolane 2,2-dioxide were purchased from Energy
Chemical. Hexamethylenetetramine was purchased from Alad-
din. Ethanol and hexane were purchased from Beijing
Reagents. Acetonitrile and triethylamine were purchased from
Xilong. All these chemicals were used without any further
purification. THF, 1,4-dioxane and toluene were treated with
calcium hydride and sodium, and distilled before use.
4.2. Synthesis and characterizations
The synthetic routes for TPE-Br, TPE-CHO, indole-SO3 and
target molecule of SPPATPE are illustrated in Scheme 1. Control
molecule of SPTPE was prepared according to the literature.38
Synthesis of TPE-Br. n-BuLi (2.5 M, 10 mmol) was added
dropwise to a THF (20 mL) solution of diphenylmethane
(17.6 g, 10.5 mmol) and allowed to react for 30 minutes to
produce an orange-red diphenyl lithium solution, and the
solution was cooled to 78 1C and 4-bromobenzophenone
(2.6 g, 10 mmol) was added. The reaction mixture was stirred
at room temperature for 6 hours, and then quenched with
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saturated NH4Cl solution and extracted with dichloromethane;
the organic phase was dried with anhydrous Na2SO4 and the
desiccant was removed by suction filtration. The solvent was
evaporated under reduced pressure to give the solid. Then the
solid was dissolved in 25 mL toluene, and a catalytic amount of
p-toluenesulfonic acid was added and allowed to reflux for
12 hours. The p-toluenesulfonic acid and the generated water
were separated by an oil–water separator. The crude product
was recrystallized from dichloromethane and methanol to give
a white powder (3.69 g). Yield: 90%.
Synthesis of TPE-CHO. 2-Hydroxy-5-(4,4,5,5-tetramethyl-
1,3,2-dioxaborolan-2-yl) benzaldehyde, 1-(4-bromophenyl)-1,2,2-
tri-phenylethene and potassium carbonate were dissolved in a
mixed solution of 10 mL degassed THF and 3 mL deionized
water. The solution was frozen with liquid nitrogen and then
Pd(Ph3P)4 was added. The flask was evacuated under vacuum
and flushed with dry nitrogen three times. After the solution was
recovered to room temperature, the reaction liquid was heated to
reflux overnight under stirring. 20 mL water was added into the
flask and extracted three times with diethylether. The organic
phase was concentrated and evaporated to remove the solvent.
The crude product was purified by fast column chromatography
(dichloromethane : hexane = 1 : 1) Yield: 76.5%. 1H-NMR
(500 MHz, CDCl3) d 10.96 (s, 1H), 9.92 (s, 1H), 7.72–7.68
(m, 2H), 7.29 (d, J = 8.2 Hz, 2H), 7.15–6.98 (m, 18H). 13C-NMR
(126 MHz, CDCl3) d 196.62 (s), 160.89 (s), 143.78–143.54 (m),
142.98 (s), 141.37 (s), 140.30 (s), 136.99 (s), 135.49 (s), 132.85 (s),
131.99 (s), 131.62 (s), 131.52–131.20 (m), 127.90–127.56 (m),
126.53 (d, J = 6.4 Hz), 125.65 (s), 120.70 (s), 118.05 (s).
Synthesis of Indole-SO3. A solution of 1,2-oxathiolane 2,2-
dioxide and indole was refluxed at 90 1C for 6 hours to obtain a
dark purple liquid. Ethyl acetate was added to the solution to
precipitate the crude product. Pure product with light pink
color was obtained by washing the precipitate with anhydrous
ether and ethyl acetate separately. Yield: 90%. 1H-NMR
(500 MHz, DMSO) d 8.05 (d, J = 6.9 Hz, 1H), 7.85–7.78 (m,
1H), 7.66–7.58 (m, 2H), 4.72–4.61 (m, 2H), 3.48 (d, J = 30.2 Hz,
6H), 2.83 (s, 3H), 2.62 (t, J = 6.5 Hz, 2H), 2.16 (dt, J = 14.2, 7.2 Hz,
2H), 1.53 (s, 6H).
Synthesis of ROF SPPATPE. TPE-CHO (0.59 g, 1.29 mmol)
and indole-SO3 (0.29 g, 1.05 mmol) were dissolved in 10 mL
ethanol solution. The flask was evacuated under vacuum and
flushed with dry nitrogen three times; then the mixture was
refluxed at 85 1C for 48 hours. After the removal of ethanol, the
rest was dissolved in the mixture of methyl alcohol and
dichloromethane solution. Then absolute ether was added to
get an orange precipitate. The product was collected by filtra-
tion and washed with ethyl acetate and absolute ether twice. An
orange solid pure product was obtained. Yield: 69%. 1H-NMR
(500 MHz, DMSO) d 11.26 (s, 1H), 8.61 (d, J = 16.3 Hz, 1H), 8.49
(s, 1H), 8.08–8.00 (m, 2H), 7.89–7.77 (m, 2H), 7.69 (d, J = 8.3 Hz,
2H), 7.66–7.59 (m, 2H), 7.20–7.08 (m, 10H), 7.07–6.98 (m, 8H),
4.82 (t, J = 7.4 Hz, 2H), 2.63 (t, J = 6.3 Hz, 2H), 2.24–2.16 (m, 2H),
1.79 (s, 6H). m/z: 716.2827.
Synthesis of RCF SPPATPE. ROF SPPATPE (1 g) was dissolved
in dichloromethane (20 mL), and then Na2CO3 aqueous
J. Mater. Chem. C, 2018, 6, 2113--2122 | 2119

Paper
solution (30 mL) was added into the flask and extracted three
Published on 25 January 2018. Downloaded by Université de Strasbourg, Service Commun de la Documentation on 1/14/2022 7:38:49 PM.
times with dichloromethane. The organic phase was dried with
anhydrous Na2SO4 and the desiccant was removed by suction
filtration. A light green solid pure product was obtained after
the solvent was evaporated. Yield: 97%.
Preparation of SPPATPE/PVP thin film. PVP (95 mg, Mn:
40 000) and SPPATPE (5 mg) were added to a mixed solution of
methanol (1 mL) and a small amount of dichloromethane. The
solution was stirred further for 2 hours to fully dissolve the
polymer. Then the solution was dropped on a glass plate and
heated at 130 1C to form an orange film with SPPATPE in their
ROF. The other two PVP films using different molecular weights of
PVP (Mn: 360 000 and 1 300 000) were prepared in the same way.
Preparation of SPPATPE/PVP/PDMS thin film. SPPATPE
(5 mg), PVP (95 mg, Mn: 40 000), silicone elastomer (990 mg) and
silicone elastomer curing agent (10 mg) were added to a mixed
solution of 1 mL methanol and a small amount of dichloromethane.
The solution was stirred until all the polymer was dissolved, and
they were placed in a vacuum oven for 15 minutes to remove
solvents. Then the sticky mixture was dropped on a glass plate
and heated at 140 1C for 30 minutes to fabricate the hybrid film.
Preparation of SPPATPE/PVP/PDMS nanofibers by electro-
spinning. SPPATPE (5 mg), PVP (245 mg Mn: 40000), silicone
elastomer (750 mg) and silicone elastomer curing agent (50 mg)
were dissolved in 1 mL methanol and a small amount of
dichloromethane. The solution was stirred until all the polymer
was dissolved. Then the precursor solution was loaded in a
plastic syringe with a 21 G needle for electrospinning. The
electrospun nanofibers were collected onto a ground aluminium
foil and were placed 15 cm away from the spinneret. The applied
voltage was 15 kV and the flow rate was about 1 mL h 1.
4.3. Instruments
1
H-NMR spectra were recorded on a 500 MHz Bruker Avance
spectrometer 13C-NMR spectra were recorded on a 126 MHz
Bruker Avance spectrometer. The deuterated solvents including
CDCl3 and [d6] DMSO were used with tetramethylsilane (TMS) as
the internal standard (d = 0.00 ppm). The nanofibers were pro-
duced by the ET-2535DC electrospinning equipment. Fluorescence
spectra of all samples (in solid and in solution) were measured
with a RF-5301PC spectrofluorometer. UV-vis spectra were mea-
sured on a Shimadzu UV-2550 spectrophotometer. Powder XRD
patterns were obtained from a PANalytical B.V. Empyrean X-ray
diffractometer with Cu-Ka radiation (l = 1.5418 Å) at 25 1C (scan
range: 5–501). MS spectrum was obtained with a ITQ1100 instru-
ment (Thermo Fisher). The absolute fluorescence quantum yields
were measured on Edinburgh FLS920 fluorometer using an inte-
grating sphere. Optical power density meter: THOR LABS Optical
Power Meter PM100A. Solar simulator: equipped with CEL-S500/
350 Xenon lamp and CEL-AM 1.5 cut-off filter, irradiation distance
was 15 cm. Photos were taken using a Canon camera.
Conflicts of interest
There are no conflicts to declare.
2120 | J. Mater. Chem. C, 2018, 6, 2113--2122
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Journal of Materials Chemistry C
Acknowledgements
This work was financially supported by the National Science
Foundation of China (51303063) and Program for JLU Science
and Technology Innovative Research Team (JLUSTIRT).
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