Loading Photochromic Molecules into a Luminescent Metal–Organic Framework for Information Anticounterfeiting

Article abstract of DOI:10.1002/anie.201910467

Stimuli-responsive photoluminescent materials have attracted considerable attention owing to their potential applications in security protection because the information recorded directly in materials with static luminescent outputs are usually visible under either ambient or UV light. Herein, we realize reversible information anticounterfeiting by loading a photoswitchable diarylethene derivative into a lanthanide metal–organic framework (MOF). Light triggers the open- and closed-form isomerization of the diarylethene unit, which respectively regulates the inactivation and activation of the photochromic FRET process between the diarylethene acceptor and lanthanide donor, resulting in reversible luminescence on–off switching of the lanthanide emitting center in the MOF host. This photoresponsive host–guest system allows for reversible multiple information pattern visible/invisible transformation by simply alternating the exposure to UV and visible light.

Full text of DOI:10.1002/anie.201910467

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
International Edition Chemie
www.angewandte.org
Accepted Article
Title: Loading Photochromic Molecule into Luminescent Metal-Organic
Framework for Potential Information Anti-counterfeiting
Authors: Banglin Chen, Zhiqiang Li, Guannan Wang, Bin Li, Yingxiang
Ye, and Huanrong Li
This manuscript has been accepted after peer review and appears as an
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201910467
Angew. Chem. 10.1002/ange.201910467
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http://dx.doi.org/10.1002/ange.201910467

Angewandte Chemie International Edition
10.1002/anie.201910467
RESEARCH ARTICLE
Loading Photochromic Molecule into Luminescent Metal-Organic
Framework for Potential Information Anti-counterfeiting
[ab]
[a]
[b]
[a]
[a]
[b]
Zhiqiang Li, Guannan Wang, Yingxiang Ye, Bin Li, Huanrong Li* and Banglin Chen*
Abstract: Stimuli-responsive photoluminescent materials have
attracted particular attention due to their potential applications in
security protection field, because the data or information recorded
directly in materials with static luminescent outputs are usually
visible under either ambient or UV light. Especially the ones with
remote control over reversible luminescence ON-OFF switch
behavior are extremely expected, as reversible visible/invisible
humans, but also inconvenient for suppliers and consumers
without professional chemistry knowledge to handle the anti-
counterfeiting operation. On the other hand, some of these
[8]
responses are irreversible.
luminescence cannot recover anymore.
information is irreversibly destroyed,
temporarily hided. In contrast, photoresponsive luminescent
As a result, the quenched
[
2a]
The encoded
rather than
information transformation can be achieved in a noninvasive manner. materials are appealing candidates, because light irradiation has
Herein, we realize reversible information anti-counterfeiting via
loading photoswitchable diarylethene derivative into lanthanide
metal-organic framework (MOF). The light triggers open and close
isomerization of the diarylethene unit, which respectively regulates
the inactivation and activation of the photochromic FRET process
between diarylethene acceptor and lanthanide donor, resulting in
reversible luminescence ON-OFF of lanthanide emitting center in
MOF host. This photoresponsive host-guest system allows for
reversible multiple information pattern visible/invisible transformation
by simply alternating the exposure to UV and visible lights.
the possibility to remote trigger cleanly and spatiotemporally
[
9]
control over the action with high precision.
Moreover,
photoswitchable materials can be reversibly interconverted
between two discrete states with drastic different optical outputs
upon alternative light trigger, showing much more convenience
in displaying or erasing the encoded information in
noninvasive manner.
a
[
10]
In terms of emitting centers, lanthanides are widely believed
to be ideal emitting sources because of their intriguing optical
properties, such as high luminescence quantum yield, long
excited lifetime, large Stokes shifts and characteristically narrow
[
11]
emissions. As an emerging class of crystalline materials that
combine the stability and porosity with the chemical tunability of
traditional organic chemistry, metal-organic frameworks (MOFs)
Introduction
[12]
have attracted vast attention in various fields.
Lanthanide
Photoluminescent materials have attracted considerable
attention due to their widely application in data recording,
MOFs, assembled by lanthanide ions with organic bridging
linkers are very promising platforms to explore versatile
[
1]
storage and security technologies. However, materials with
static luminescent outputs are adverse to their practical
application in confidential information protection, because the
data or information recorded directly in these materials are
usually visible under either ambient or the excitation of NIR or
[11d, 13]
luminescent materials.
The emission colors, excitation
bands as well as pores/channels can be finely tuned by varying
[14]
the lanthanide ions and organic linkers.
Intelligent MOF
materials with remote-controllable capacity can be achieved by
[
15]
[
2]
incorporating photoswitchable molecules.
However, besides
UV light. In this context, smart luminescent materials, which
can change their luminescent outputs in response to external
stimuli, and possess extra security features, have been regarded
as ideal alternate candidates to prevent tampering or
tedious synthesis of organic linkers, directly integrating
photochromic units as part of the linker molecules and
incorporating them into the backbone of MOF structures also
usually lead to limited isomerization yield and slow isomerization
speed, since isomerization are hindered in the rigid crystalline
[
3]
counterfeiting. Amongst them, the ones with luminescence
ON-OFF switch behavior are extremely interesting, as reversible
visible/invisible information transformation can be achieved. In
this case, the information pattern is usually invisible under
normal condition, while only become visible when needed,
making it nearly impossible to mimic and counterfeit. In recent
[
16]
frameworks.
Recently, encapsulating functional guest
molecules into porous MOFs has been proved to be a feasible
strategy to boost the application of MOFs by us and other
[
17]
groups.
Several photoswitchable molecules were also
[
4]
[5]
encapsulated into the cavity of MOFs to adjust their flexibilities
years, thermal-responsive, chemical-responsive, mechanical-
[
18]
[
6]
[7]
and adsorption behaviors, etc. To the best of our knowledge,
there is only one report about loading photochromic molecule
into MOFs cavity for data storage. However, it still need the co-
stimulation of light and heat with harsh condition for long time to
realize transformation between two different emission
responsive and electrochromic luminescent materials have
been explored. However, these stimuli-responsive luminescent
materials either rely on constant addition of chemicals or require
invasive stimuli, which are not only harmful to environment and
[
19]
wavelengths, rather than ON-OFF switch.
Therefore,
[
a]
Dr. Z. Li, G. Wang, B. Li, Prof. Dr. H. Li
photoswitch loaded luminescent MOFs with information
protection property capable of being easily operated in a
noninvasive manner are still highly desired.
Herein, we demonstrate an approach to realize reversible
confidential information protection based on remote control over
photoresponsive luminescence ON-OFF of photoswitch loaded
lanthanide MOF. Diarylethene is chosen as photoswitch, since it
is regarded as the shining star in photochromic realm due to its
thermal irreversibility and excellent fatigue resistance, high
Tianjin Key Laboratory of Chemical Process Safety, School of
Chemical Engineering and Technology, Hebei University of
Technology, Tianjin 300130, P. R. China.
E-mail: lihuanrong@hebutedu.cn
Dr. Z. Li, Y. Ye, Prof. Dr. B. Chen
Department of Chemistry, University of Texas at San Antonio, San
Antonio, TX 78249, USA.
E-mail: banglin.chen@utsa.edu
Supporting information for this article is given via a link at the end of
the document.
[
b]
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Angewandte Chemie International Edition
10.1002/anie.201910467
RESEARCH ARTICLE
3
+
3+
speed photoresponse, and good performances in both solution
emission of Eu , leading to the luminescence quench of Eu
attributed to the activation of the photochromic fluorescence
[
20]
and solid phase.
To transfer the reversible ring-closing and
3
+
ring-opening isomerization of diarylethene unit to the
resonance energy transfer (FRET) between Eu
and
3
+
luminescence switching, Eu
ion possessing spectral
diarylethene. As a result, the security code becomes invisible
and unreadable. Hence, the photo triggers open and close
isomerization of the diarylethene unit, and thus regulates the
inactivation and activation of the FRET process, resulting in a
reversible luminescence ON-OFF switch of Eu emitting center
in the diarylethene loaded lanthanide MOF, which is capable of
conducting reversible multiple security data protection.
overlapping with the diarylethene isomer is introduced to
construct the host luminescent MOF. For example, there is no
spectral overlap between the absorption band of the open form
3
+
3+
diarylethene and the emission band of Eu , the host MOF
3
+
exhibits characteristic emission of Eu
and the encoded
information is readable. While there is perfect spectral overlap
between the absorption of close form diarylethene and the
Figure 1. Schematic illustration of photochromic DAE chromophores incorporated into ZJU-88, and photoswitchable isomerization behavior of ZJU-88⊃OF-DAE
under alternating UV and visible light irradiation.
Results and Discussion
ZJU-88⊃OF-DAE didn't decreased
a
lot, and all the
characteristic peak of ZJU-88 were maintained. This
phenomenon revealed that the vast majority of frameworks were
retained after loading. Besides, characteristic vibration peaks of
OF-DAE was observed in the FT-IR spectra of ZJU-88⊃OF-
DAE (Figure S2). S element was also detected in elemental
analysis of ZJU-88⊃OF-DAE (Table S1). These results
indicated that DAE had been successfully loaded into MOF host.
To distinguish whether DAE was loaded into the MOF pores or
adsorbed on the MOF surface, we carried out the following
control experiment: ZJU-88 and OF-DAE were individually
ground for 2 h, and then mixed without further grinding, washed
repeatedly with EtOH. We then monitored the UV-Vis absorption
spectra of the wash filtrate of both ZJU-88⊃OF-DAE and the
control group (Figure S3). The results revealed that the DAE in
the eluate of ZJU-88⊃OF-DAE was in two states (in pores and
surface adsorbed), while the DAE in that of the control group
was in one state (surface adsorbed). In addition, the surface
adsorbed DAE can be completely washed away in three times
Host MOF ZJU-88 with
a
chemical composition of
OH) was prepared by
[
Eu
reaction
tetracarboxylic acid (H
2
(QPTCA)(NO
3
)
2
(DMF)
4
]·(CH
3
CH
2
3
of
1,1′:4′,1′′:4′′,1′′′-quaterphenyl-3,3′′′,5,5′′′-
QPTCA) with Eu(NO according to our
4
3 3
)
[
21]
previous method. The crystal of ZJU-88 has one-dimensional
2
channels along the c-axis of about 8 × 12 Å , which are large
enough to encapsulate
1,2-Bis(2-methyl-5-(4-formylphenyl)-
thiophen-3-yl)hexafluorocyclopentene (OF-DAE) (23.38 ×8.98 ×
[
22]
7
.75 Å) molecules (Figure S1).
obtained as white powder after loading OF-DAE into ZJU-88
see Experimental Section in supporting information). Powder X-
ZJU-88⊃OF-DAE was
(
ray diffraction (PXRD) after loading showed that the 2θ positions
of all characteristic reflections remain unchanged compare to
ZJU-88 (Figure 2), demonstrating the retention of crystalline
MOF backbone. The PXRD signal/noise ratio became lower
after loading, in addition to decreased size, this may be also
attributed to partial framework defects induced by mechanical
force. However, compare to ZJU-88, the PXRD peak intensity of
1
(Figure S3B and 3D). H NMR spectra (Figure S4A) of acid
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RESEARCH ARTICLE
digested ZJU-88⊃OF-DAE revealed the molar ratio of H
to DAE is about 7 (Eu : DAE =14:1), which is consistent with
4
QPTCA
We then investigated the photoluminescence behaviors of
3
+
the host-guest system. The excitation spectrum of ZJU-88⊃OF-
5
7
that obtained by elemental analysis (Table S1). while no obvious
DAE by monitoring the D
in the range of 250-400 nm, corresponding to the absorption of
4
H QPTCA ligands, and thus indicates the occurrence of energy
0 2
→ F transition showed a broad band
1
DAE peaks were observed in the H NMR spectra of the control
group after washing for three times (Figure S4B). Meanwhile,
compare to ZJU-88, the DMF content in ZJU-88⊃OF-DAE
underwent an obvious decrease (about 53.3% according to the
[
23]
transfer from ligand to metal (Figure S7). When excited at 350
nm, the emission spectrum of ZJU-88⊃OF-DAE powder
displayed five sharp peaks at 579, 590, 613, 650, and 698 nm,
1
H NMR integral data), implying that the included solvent had
5
7
been partially squeezed out the channel of ZJU-88 host by the
guest molecules (Figure S5). In order to further obtain molecular
level information of ZJU-88⊃OF-DAE, we measured the survey
XPS spectra of both ZJU-88 and ZJU-88⊃OF-DAE surface
attributing to the D
0
7
→ F
J
(J = 0‒4) transitions. Amongst these
5
peaks, the
0 2
D → F
band at 613 nm is predominantly
responsible for the emission color in red. The quantum yield of
ZJU-88⊃OF-DAE was determined to be 7.16%, indicating
sufficient brightness for luminescent applications.
(
Figure S6). The presence of F 1s and S 2p peaks in ZJU-
8⊃OF-DAE XPS spectra confirmed the existence of DAE in the
8
Next, we investigated the photoresponse of ZJU-88⊃OF-
DAE as a result of the isomerization of DAE moieties. Before
host-guest complex. We then etched ZJU-88⊃OF-DAE to 20 nm
depth and collected the elemental composition of 20 nm depth,
where F 1s and S 2p peaks were also detected. This result
demonstrated that DAE also existed in the MOF pores, rather
than simply adsorbed on the MOF surface. More importantly, the
F and S contents at 20 nm depth were slightly higher compare to
the ZJU-88⊃OF-DAE surface. This can be explained as follow:
although the DAE at outer wall of MOF has been wash away,
the surface XPS test usually penetrate and collect elemental
information of the superficial several nanometers, rather than the
outermost surface. However, DAE at the outer wall of MOF had
been wash away, as a result, the F and S contents of the
surface test is only slightly lower than that of 20 nm depth.
These results also provided powerful evident that DAE had been
successfully loaded into the MOFs host. Moreover, XPS
scanning at different areas of ZJU-88⊃OF-DAE showed similar
element composition, revealing that DAE guest distributed
homogeneously in ZJU-88⊃OF-DAE crystal blocks. These
results jointly confirmed that the OF-DAE molecules have been
embedded within ZJU-88.
1
loaded into ZJU-88, UV–Vis (Figure S8) and H NMR spectra
(Figure S9) revealed individual DAE underwent reversible open
and close isomerization quantitatively upon alternating exposure
[
24]
to UV and visible light. In the as-prepared ZJU-88⊃OF-DAE
white powder, since DAE was in the open configuration and
showed the absorption below 400 nm, there was no spectral
overlap between the emission of ZJU-88 and the absorption of
OF-DAE (Figure 3A). As a result, ZJU-88⊃OF-DAE exhibited
3+
the characteristic color and brightness of Eu ions under 365
nm light, as no FRET occurred. After irradiated with 300 nm UV
light, the white host-guest inclusion complex turned to blue. This
is because DAE switched from open form (OF-DAE) to close
form (CF-DAE) with a new absorption band in the range of 500-
700 nm, which is perfectly overlapped with the emission
spectrum of ZJU-88 host (Figure 3A). Meanwhile, the
luminescence of ZJU-88⊃CF-DAE quenched gradually and
reached to the equilibrium in 60
s (Figure 3B). The
luminescence quenching followed a biexponential attenuation
law (Figure S10), underwent a fast process, followed by a slow
process to the photo steady state. At the end point, the
luminescence intensity was quenched by 91% with concomitant
decreases of the decay from 540 μs to 65 μs (Figure S11).
These observations jointly indicated the occurrence of the FRET
3
+
from the Eu donor in ZJU-88 to the CF-DAE acceptor. The
FRET efficiency (E) was calculated to be 88% according to the
[
25]
reported methods.
To be noticed, the confinement of DAE
within the ZJU-88 is essential to draw the donor and acceptor in
close proximity, which plays vital role in facilitating high
[
26]
efficiency FRET. Non-porous Eu/2,6-pyridinedicarboxylic acid
[
27]
3
complex Eu(PDA) , which also has spectral overlap with CF-
DAE, was taken as a model compound and mixed with OF-DAE
in EtOH. However, after irradiated with 300 nm UV light for 60
seconds, no effective FRET was observed in the mixture (Figure
S12). Interestingly, upon subsequent irradiation with visible light
(
λ > 450 nm), the luminescence of quenched ZJU-88⊃CF-DAE
Figure 2. PXRD patterns of ZJU-88, and ZJU-88⊃OF-DAE before and after
recovered in 90 s and the PL intensity reached to 96% of the
original value accompanied with the color change back to white,
arising from the reverse photoisomerization back to OF-DAE
(ZJU-88⊃CF-DAE) irradiated with 300 nm UV light for 60 seconds.
(
Figure 3C). The fatigue resistance of ZJU-88⊃DAE was further
examined after 20 consecutive cycle irradiation of UV (300 nm,
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Angewandte Chemie International Edition
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RESEARCH ARTICLE
6
0 s) and visible light (> 450 nm, 90 s), and the results are
system, which are of utmost important for photochromic optical
memory and data storage materials.
shown in Figure S13. Negligible decrease in PL intensity was
observed, implying excellent fatigue resistance of our host-guest
Figure 3. (A) Normalized emission spectra of ZJU-88⊃OF-DAE (a), as well as absorption spectra of OF-DAE (b) and CF-DAE (c). (B) Luminescence emission
spectra (λex = 350 nm) and emission intensity changes at 613 nm (inset) of ZJU-88⊃OF-DAE upon 300 nm UV light irradiation. (C) Luminescence emission
spectral intensity and emission intensity changes at 613 nm (inset) of ZJU-88⊃CF-DAE upon subsequent irradiation with visible light (> 450 nm). (D) The
photographs of ZJU-88⊃OF-DAE under daylight (i) and 365 nm UV lamp (ii), under daylight (iii) and 365 nm UV lamp (iv) after irradiated with UV light for 60s.
1
stable OF-DAE (Figure S15). In the H NMR spectra (Figure 5),
after 300 nm UV light irradiation, the thiophene protons (H
showed drastic upfield shift from 7.74 ppm to 7.18 ppm, while
the methyl protons (H ) also showed downfield shift from 2.03
ppm to 2.13 ppm. Meanwhile, the aldehyde proton (H
underwent downfield shift from 10.01 ppm to 10.08 ppm.
However, it was difficult to monitor the chemical shifts of H and
due to the signal overlap with H and H protons of H QPTCA.
b
)
a
e
)
c
H
d
3
4
4
All these shifts were complete and negligible signals were
observed in the original chemical shifts of OF-DAE, indicating
quantitative transition from OF-DAE to CF-DAE in this solid
host-guest inclusion complex. The open to close form photo-
isomerization yield was calculated to be 95.2% according to the
Figure 4. Schematic illustration of the photo triggered luminescent ON-OFF
switch behavior of ZJU-88⊃OF-DAE under alternating UV and visible light
irradiation
1
[24a]
integral of H NMR , which is much higher than that directly
[
16b]
integrating DAE as MOFs backbone
and is as good as
1
UV-Vis and H NMR spectra provided important insight into
that of diarylethene derivative monomers in other host-guest
[10a, 28 ]
the nature of the light-triggered luminescence ON-OFF switch of
system.
host-guest inclusion complex. After photo-irradiation of ZJU-
88⊃OF-DAE with 300 nm UV light, the resulting blue powder
was digested by hydrochloric acid and diluted by DMSO, then
monitored by UV-Vis analysis (Figure S14). The absorption peak
at 330 nm decreased and the absorption at 607 nm increased,
which explained the color change from white to blue, indicating
the successful transformation to inherently thermal and daylight
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Angewandte Chemie International Edition
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RESEARCH ARTICLE
quenched ZJU-88⊃CF-DAE pattern was also very stable, which
was still invisible under both daylight and UV lamp during this
period (Figure S19). Subsequent recognition process (video S4)
can be conducted remotely by exposing the hidden pattern to
visible light (>450 nm). This remote light-triggered reversible
information hiding and recognition process showed good fatigue
resistance and still remained unaffected even after 20
consecutive switching cycles (video S5), implying that our
platform is suitable for multiple information anti-counterfeiting.
1
Figure 5. Partial H NMR spectra of OF-DAE (A), ZJU-88⊃OF-DAE (B), ZJU-
4 6
88⊃CF-DAE (C) and H QPTCA in DCl/DMSO-d (1:10, v:v) at 25 °C.
Encouraged by the above findings, we designed a novel
strategy for information coding and anti-counterfeiting by using
this host-guest complex as invisible security ink. Various
patterns with good resolution were obtained by spraying ZJU-
88⊃OF-DAE ethanol suspension on filter paper with hollow out
stencils, including the logo of Hebei University of Technology
and QR code. For the sake of illustration, we programed the
information in the QR code and loaded it to the website of our
University. The logo was invisible under daylight (Figure S16A),
and became visible under commercial portable UV lamp (365
nm), allowing for readout the stored information. Then we tried
to erase the pattern with 300 nm UV light. After irradiating, the
luminescence of the pattern quenched and cannot be read out
anymore under the UV lamp, but the pattern turned to blue and
became visible under daylight, failing in confidential information
hiding (Figure S16C). In order to develop hidden label, we took
blue filter paper with negligible auto fluorescence as the
Figure 6. Light-triggered reversible information anti-counterfeiting behaviors of
the host-guest complex. Photographs of the ZJU-88⊃OF-DAE luminescent
QR code on blue filter paper (size: 6 × 6 cm) upon alternating UV (300 nm, 60
sec) and visible light (>450 nm, 90 sec) irradiation under daylight (A, C) and
365 nm UV lamp (B, D). Photographs of QR code before (Figure 6A, 6B) and
after (Figure 6C, 6D) irradiated with 300 nm UV light.
background (Figure 6 and Figure S17). The pattern was also Conclusion
invisible under daylight (Figure 6A and video S1) and readable
under UV lamp by WeChat (Figure 6B and video S2), a
commercially available smartphone app has more than one
billion users in China, despite the luminescence intensity was
lower than that on white filter paper. To be noticed, the main
absorption band of OF-DAE peaked at 330 nm and the
absorption at 365 nm was relatively weak (Figure S8). As a
result, the light-triggered transformation process from OF-DAE
to CF-DAE was slow under 365 nm UV lamp, which allowed
enough time for the the coding information to be read out. Upon
irradiated with 300 nm UV light, the quenched luminescence and
blue background jointly promoted the really invisible (video S3)
characteristic of ZJU-88⊃CF-DAE patterns (Figure 6C and 6D),
which is essential and necessary for confidential information
anti-counterfeiting. The erased pattern was very stable under
daylight due to the thermal irreversibility nature of DAE
derivatives, and remained unreadable even after several months.
No obvious automatic recovery in UV–Vis spectra of both ZJU-
In conclusion, we reported an approach to realize potential
confidential information protection based on the solid state
photoresponsive luminescence ON-OFF switch behavior of
photochrome loaded lanthanide MOF. Owing to the FRET
between Eu metal center and photochromic unit governed by the
light triggered open and close isomerization of DAE, it was
loaded into ZJU-88 to produce photoswitchable luminescence
host-guest complex. The information recorded in this anti-
counterfeiting system could be precisely concealed and read out
by simply alternating the irradiation with UV and visible light in a
very short time, making it extremely attractive and suitable as
the next generation of intelligent information protection material.
As the emission and excitation wavelengths, pore sizes of MOFs
host could be precisely tailored through the appropriate choice
of various metal centers and organic linkers, this will nodoubt
allow the MOFs host to load various photoswitchable molecules
with diverse emission wavelengths. We believe this remote light
triggered host-guest strategy will offer new insights in
broadening the practical applications of MOFs.
88⊃CF-DAE (Figure S15) and CF-DAE (Figure S18) were
observed after being placed under daylight for months. The
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RESEARCH ARTICLE
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and the Program for Top 100 Innovative Talents in Colleges and
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The authors declare no conflict of interest
Keywords: metal-organic framework • lanthanide •
photoswitchable • host-guest system • information anti-
counterfeiting
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Angewandte Chemie International Edition
10.1002/anie.201910467
RESEARCH ARTICLE
RESEARCH ARTICLE
We realize reversible confidential
information protection via loading
photoswitchable molecule into
Z. Li, G. Wang, Y. Ye, B. Li, H. Li* and
B. Chen*
lanthanide MOF. The light triggered
open and close isomerization of the
diarylethene unit regulates
Page No. – Page No.
Title
luminescence ON-OFF switch of
lanthanide emitting center, allowing for
reversible multiple information anti-
counterfeiting by simply alternating the
exposure to UV and visible lights.
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