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Reversible photochromic tetraphenylethene-based Schiff base:
Design, synthesis, crystal structure and applications as visible
light driven rewritable paper and UV sensor
Hao Sun a, Jing-Yang Li a, Fang-Fang Han a, Ran Zhang *a, Yun Zhaoa, Bao-Xi Miao a
and Zhong-Hai Ni*a
a School of Chemical Engineering and Technology, China University of Mining and
Technology, Xuzhou, 221116, People’s Republic of China
Corresponding author E-mail: [email protected] (R. Zhang) and
[email protected] (Z. H. Ni)
Contents
1. Crystal data of TPENOEt
2. Crystal packing diagrams of TPENOEt
3. The influence of different wavelength light on the color change of TPENOEt
4. Fatigue resistance
5. AIE property of TPENOEt
6. Absorption spectra of TPENOEt before and after UV light irradiation in
different solvents
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7. Write-erase process
8. The prepartion of the portable rewritable paper
9. Application as UV sensor
10. 1H NMR, 13C NMR and MALDI TOF-MS spectrum of TPENOEt
1. Crystal data of TPENOEt
Table S1 Crystal data and structure refinement of TPENOEt
Empirical formula C35H29N1O2 Dc/(g·cm-3) 1.227
Formula weight 495.59 Z 4
T/K 293(2) μ/mm-1 0.075
Crystal system Monoclinic F(000) 1048
Space group P21/c range for data collection/o 1.85-25.00
a/(Å) 15.864(9) Reflections with I> 2(I) 1968
b/(Å) 15.628(10) GOF on F2 0.972
c/(Å) 11.056(7) R1 (I> 2(I)) 0.0518
β/(o) 101.865(13) wR2 (all data) 0.0839
V/Å3 2682(3)
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2. Crystal packing diagrams of TPENOEt
C
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Figure S1 Crystal packing diagrams (A and B) and structure (C) of compound TPENOEt.
3. The influence of different wavelength light on the color change of TPENOEt
Table S2 The influence of different wavelength light on the color change of
TPENOEt.
Wavelength/nm 300 330 360 390 410 420 450 480 510 540 590
Color change Ya Y Y Y Y Y N N N N N
Color recovery Nb N N N Y Y Y Y Y Y Y
a: Y = Yes; b N = No.
4. Fatigue resistance
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Figure S2 Fatigue resistance of TPENOEt upon UV light and white light irradiation
alternatively. λ = 600 nm, UV light: 365 nm.
5. AIE property of TPENOEt
We explored the AIE property of TPENOEt, its fluorescence property in THF with
different water contents were performed. TPENOEt is highly soluble in THF, but
poorly dissolves in water. The fluorescence spectra obtained from the test is shown in
Fig. S3. TPENOEt was nearly no emission in pure THF, and the fluorescence
emission was very weak before the water fraction up to 60%. With the increase of
water content in THF, the fluorescence emission started to increase when the water
content reached 70%, indicating that molecules gradually aggregated to form invisible
nanoparticles. After that, the emission of TPENOEt sharply increases with further
increasing the water fraction until the measured water fraction of 90%. These results
indicates that TPENOEt is typical AIE compound. The fluorescence intensity of
TPENOEt in THF/water mixture was very weak even though the water content
reached 90%. This may be attributed to the effect of electron-donating group on the
phenol ring and the formation of trans-keto form which considred to be the final
photochromic product and resulted from nonradiative deactivation of cis-keto.
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Figure S3 (A) PL spectra of TPENOEt in H2O/THF mixtures with different water
fractions. (B) Changes in PL peak intensity with water fractions, the data are extracted
from (A). For PL measurement, TPENOEt concentration: 10-5 M, excitation
wavelength: 480 nm.
6. Absorption spectra of TPENOEt before and after UV light irradiation in
different solvents
Figure S4 Absorption spectra of TPENOEt before and after UV light irradiation in
(A) Hex (n-hexane), (B) THF (tetrahydrofuran), (C) DCM (dichloromethane), (D)
MeCN (acetonitrile).
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7. Write-erase process
Figure S5 Letter “Z” is written on and erased from TPENOEt.
Figure S6 The irradiated TPENOEt acts as a rewritable paper.
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8. The preparation of the portable rewritable paper and write-erase process
The prepared paraffin wax is heated to 80 ℃，and then, TPENOEt is added into the
melted paraffin. The above mixture is thoroughly stirred to make TPENOEt
uniformly disperse in the paraffin solution. Then, the mixture is injected into a
silicone mold that has been preheated to 80 ℃. Finally, the system is cooled down
to room temperature to generate the rewritable paper.
Figure S7 The writing and erasing process carried out on the constructed “paper”.
9. Application as UV sensor
The atmospheric ozone layer plays vitally important role in protecting humans,
animals and plants on earth from UV damage. However, the ozone layer has been
seriously destroyed due to various reasons, which results in increasingly serious UV
radiation pollution. Excessive UV radiation will lead to an additional risk of skin
cancers, decreased immunity and cataracts, etc., therefore, the detection of UV light
becomes more and more significant. The UV radiation that reaches the earth’s surface
is composed of large fraction of UVA (315-400 nm) and about 10% UVB (280-315
nm) according to the definition of UV radiation by the world health
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organization(WHO). As described above, the UV light with the wavelength in the
range from 310 nm to 410 nm can result in the photochromism of TPENOEt. The
wavelength range agrees well with UVA range, which enables TPENOEt to be used
as a UV sensor. As is shown in Figure S7, TPENOEt exhibits different intensities of
color changes under different UV radiant intensities as monitored by a commercial
UV 340A meter. Therefore, TPENOEt can be used as a UV strength sensor naked
eye detection of UV radiation pollution.
Figure S8 TPENOEt was exposed under different radiant intensity of 365 nm UV
light. Radiant intensity from A to E: 0, 50, 100, 150, 200 μW/cm2. Exposure time: 2
min.
10. 1H NMR, 13C NMR and MALDI TOF-MS spectrum of TPENOEt
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Figure S9 1H NMR spectrum of TPENOEt.
Figure S10 13C NMR spectrum of TPENOEt.
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495.
858
0.0
0.5
1.0
1.5
4x10
Inte
ns. [
a.u.
]
490.0 492.5 495.0 497.5 500.0 502.5 505.0 507.5 510.0 512.5 515.0m/z
Figure S11 MALDI TOF-MS spectrum of TPENOEt.
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