Exploring highly efficient light conversion agents for agricultural film based on aggregation induced emission effects

Article abstract of DOI:10.1039/c6tc04215e

Aggregation-induced emission (AIE) is a unique photo-physical phenomenon that has become an emerging and hot research area. It has a wide range of applications due to its excellent luminous properties. In this paper, five compounds and their corresponding light conversion films were prepared based on AIE effects and the thermally activated delayed fluorescence (TADF) phenomenon. Furthermore, ultraviolet conversion, dispersion and photo-physical properties such as UV-vis spectra, fluorescence spectra, and photo stability as well as the mechanical properties of the light conversion films were investigated in detail. The results reveal that triphenylacrylonitrile (TPA) exhibits excellent photo stability and ultraviolet light conversion properties. In addition, the fluorescence emission spectrum of TPA corresponds well with the absorption spectrum of plants in the blue-violet region. In particular, the light conversion film with added TPA also shows enhanced mechanical properties and slightly lower visible light transmittance (3.79%) compared to PVC blank film. Based on the photo stabilities of the five compounds, it can be concluded that the electron-withdrawing cyano group can increase the photo stability of TPA, while carbazole substituents are proved to have an uncertain effect on the rate of photo oxidation, which is attributed to the electron-donating properties of carbazole and increased molecular distortion or rigidity. Finally, it is worth mentioning that this is the first report utilizing AIE-active luminogens (AIEgens) in agricultural light conversion film.

Full text of DOI:10.1039/c6tc04215e

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Nguyên T. K. Thanh, Xiaodi Su et al.
Fine-tuning of gold nanorod dimensions and plasmonic properties using
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Exploring the high efficient light conversion agents for agricultural
film based on aggregation induced emission effects
Received 00th January 20xx,
Accepted 00th January 20xx
Yunpeng Qi, Yongtao Wang,* Yongjiang Yu, Zhiyong Liu, Yan Zhang, Yu Qi and Changtong
Zhou
DOI: 10.1039/x0xx00000x
Abstract: Aggregation-induced emission (AIE) is a unique photo-physical phenomenon and has become an emerging and
hot research area. It has a wide range of applications for its excellent luminous. In this paper, five compounds and their
corresponding light conversion films were prepared based on AIE effects and thermally activated delayed fluorescence
(TADF) phenomenon. Further, ultraviolet conversion, dispersion and photo-physical property such as UV-vis spectra,
fluorescence spectra, photo stability as well as mechanical property of light conversion films were investigated in detail.
The results reveal that triphenylacrylonitrile (TPA) exhibits excellent photo stability and ultraviolet light conversion
property. In addition, the fluorescent emission spectrum of TPA corresponds well with the absorption spectrum of the
plants at blue-violet region. Especially, light conversion film added TPA also shows enhanced mechanical property and
slightly lower visible light transmittance (3.79%) than PVC blank film. Based on photo stability of five compounds, it can be
concluded that the electron-withdrawing cyano group can increase photo stability of TPA, while carbazole substituents are
proved to be uncertain to the rate of photo oxidation, which is attributed to electron-donating property of carbazole and
increased molecular distortion or rigidity. Finally, it is worth mentioning that utilizing AIE-active luminogens (AIEgens) in
agricultural light conversion film field is first time.
www.rsc.org/
fluorescence matching with crops absorption spectrum. Thus,
research and exploitation of the novel high-efficient light
conversion agents are also urgent.
Introduction
As the old saying goes, “All life on our earth depends on the
sun ". Through plant photosynthesis, crops can convert carbon
dioxide and water into human foods. However, not all sunlight
are beneficial to plant photosynthesis, among them, the blue-
violet light (400-480 nm) and red-orange light (600-700 nm)
are beneficial to plant growth and development, while the
yellow-green light (510-580 nm) are almost reflected
completely by plants leaves, the ultraviolet (280-380 nm) light
not only can increase plant diseases and insect pests, but also
lead to oxidative degradation of agricultural polyethylene film.
To make full use of solar energy, it is an important and
challenging task for the light conversion agents by converting
ultraviolet and yellow-green light into blue-violet and red-
orange light respectively. Experiments of the light conversion
film for crops on farmland show that: the light conversion
agricultural films can shorten the growth cycle of crops,
Fortunately, an interesting phenomenon, aggregation induced
emission (AIE) effect, was discovered by Tang et al research
team in 20015, 6, the AIE luminogens does not emit light or
emit faint light in solution, however, the compounds emit
strong fluorescence at aggregate state or solid state. Beyond
all question, taking full advantage of the solid-state
fluorescence emission enhancement characteristics, AIE
luminogens are expected to be excellent light conversion
agents used in agricultural film. Currently, AIE-active
luminogens have become a hot research topic for their
potential application in various fields, such as light emitting
diodes7-11
, , optical
light-harvesting12, optical storage13-18
memories19-21, mechanical sensors22, 23, chemosensing and
bioimaging24-29. Besides, AIE materials systems have been
developed such as hexaphenylsilole5, pyran derivatives30-34
,
9,10-disubstituted anthracene derivatives35-38, difluoroboron
avobenzone39-45, tetraphenylpyrazine46, 47, tetraphenylethene
(TPE)48-58, triphenylacrylonitrile (TPA)59-61. Among of them, TPE
and TPA are the most famous AIE luminogens and building
block for the construction of AIE fluorophores because of
propeller-shaped non-planar molecule conformation, facile
synthesis and excellent AIE effect. Therefore, in this paper, five
AIE-active compounds and a synthetic intermediate, named
successively TPE, TPA, DTBE-TPE, TTBC-TPE and DTBC-DPK,
were synthesized. Furthermore, a series of tests including the
light stability in solution and polyvinyl chloride (PVC) film,
increase yield of crops, and improve quality of crops1-4
However, the existing light conversion agents have such
drawbacks as single light conversion, poor stability, unsuitable
.
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ultraviolet conversion, dispersion state in PVC film as well as
corresponding mechanical properties were studied. As far as
our knowledge, this is the first report of AIE-active light
conversion agents for the purpose of agricultural application.
Results and discussion
Photophysical Properties
The UV-vis absorption spectra of TPE, TPA, DTBC-DPK, TTBC-
TPE and DTBC-TPE in dilute THF solution (1×10-5 mol/L) and
PVC films (addition of 1% by weight of AIE luminogens to PVC)
are investigated, as shown in Fig. 1. DTBC-TPE, TTBC-TPE and
DTBC-DBK emerge three absorption bands, TPE and TPA give
two absorption bands at ultraviolet region in THF solvent.
Different from the UV-vis absorption in THF solvent, the
ultraviolet absorption region of the luminogens in PVC films
are expanded. Meanwhile, the blank PVC film showed little
absorption. Consequently, we can tentatively draw the
following conclusions, the increase of ultraviolet absorption
region are not directly origin from PVC films, but due to the
change of peripheral environment of the AIE luminogens. On
the other hand, It also preliminary indicates that these AIE
luminogens are suitable as light conversion agents owe to the
excellent ability to absorb ultraviolet light.
Fig. 3 Fluorescence spectra of TPE, TPA, DTBC-DPK, TTBC-TPE
and DTBC-TPE in PVC films (a) and solid state (b). Inset:
normalized fluorescence spectra of them in PVC films (1%
mass fraction).
is almost no distinction compared to solid state, this may be
due to the fact that TPA retains similar morphology in solid
state and PVC film.
TPE, TPA, DTBC-DPK, TTBC-TPE and DTBC-TPE are all exhibit
AIE-activity, however, their fluorescence emission properties
are quite different. As shown in the Fig. 3, TTBC-TPE and DTBC-
TPE give strong emission intensity at maximum wavelength of
483 nm and 462 nm in PVC film, respectively. The fluorescence
emission peak of TPE and TPA located at 478 nm and 430 nm,
respectively, while the fluorescence intensity was declined
compared with TTBC-TPE and DTBC-TPE, the possible reason is
that the decreasing molecular conjugation is not beneficial to
electron transfer and transition. More seriously, there is
almost no fluorescence is observed for DTBC-DPK. Combining
with the intense fluorescence emission of DTBC-DPK in solid
crystalline state or aggregate state, we have reason to suspect
that DTBC-DPK is hold the amorphous state in PVC film, the
amorphous state leads to relatively weak intermolecular force,
increasing intramolecular rotations and stretching vibration,
which cause the energy relaxation via non-radiative channel,
subsequently, the above sharp fluorescence quench
happened. Therefore, it is obvious that PVC matrix can affect
the fluorescence intensity of luminogens, but whether
different impacts are also exist in the emission wavelength? By
compared with fluorescence emission spectra in solid state,
the emission peak of TPE, DTBC-DPK and TTBC-TPE showed a
red shift of 23 nm, 40 nm and 11 nm in the PVC film,
respectively. By contrast, TPA and DTBC-TPE show a blue shift
of 31 nm and 13 nm in PVC film, respectively. The shift of
fluorescence emission peak is usually related to the different
molecular packing or crystalline morphologies. However, the
packing or morphology is difficult to be predicted. Further, the
shifts of the emission wavelength of the corresponding PVC
films are investigated by thermal treatment. As a result, there
are almost no change in their emission wavelength after
In order to further understand the Light conversion behaviour
of the AIE luminogen, take an example, the excitation
spectrum of TPA in PVC film and solid state are tested. As
shown in the Fig. 2, the excitation intensity scopes almost
cover the whole ultraviolet region and exhibit two main
excitation bands at wavelength of 280 nm and 360 nm, which
Fig. 1 UV-vis absorption spectra of five compounds in THF (a)
and PVC film (b).
heated two hours at 120
℃
for these PVC films except DTBC-
DPK is observed to be blue shifted (
∼
16 nm). It is probably due
Table 1. Fluorescence emission wavelength of five compounds
at different state.
Wavelength (nm)
Entry In PVC film Ssa Asb
Width of half peak (nm)
In PVC film
Ssa
83
88
55
70
80
TPE
TPA
478
430
455 465
461 400
452 485
472 508
475 497
115
62
DTBC-DPK 492
TTBC-TPE 483
DTBC-TPE 462
102
71
Fig. 2 The excitation spectrum of TPA in PVC film and solid
state (emission wavelength: 420 nm).
81
aSs:Solid state of compounds; bAs: Aggregation state of compounds.
2 | J. Name., 2012, 00, 1-3
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to the DTBC-DPK keep a thermodynamic metastable state in
PVC film. In addition, the width of half peak (FWHF) is also an
important parameter. Generally, the bigger is FWHF, the less
uniform is crystal particles. As shown in Table 1, the FWHF is
increased after dispersed the light conversion agents in PVC
films for TPE and DTBC-DPK, no obvious change for TTBC-TPE
and DTBC-TPE, and decreased for TPA, which further indicate
that TTBC-TPE, DTBC-TPE and TPA also maintain excellent
crystal state, while TPE and DTBC-DPK transformed to
amorphous state from crystal state in PVC films. Based on the
data from UV-vis absorption spectra, excitation spectra and
fluorescence spectra, TPE, TPA, DTBC-DPK, TTBC-TPE and
DTBC-TPE could efficiently convert the ultraviolet light into
blue light in both solution and PVC films, and their
fluorescence emission spectra could match with blue light
region of plant photosynthesis. Compared with TPE and DTBC-
DPK, TPA, DTBC-TPE and TTBC-TPE are the better light
conversion materials using for agriculture film.
In order to evaluate the photo stability of five luminogens, the
fluorescence spectra of them in PVC films are recorded under
artificial sunlight irradiation at different times. As shown in Fig.
S1 and Fig. S3, the fluorescence emission peak of TPE films has
no obvious changes after exposed to photo irradiation two
hours, after radiated three hours, the fluorescence intensity
began to decrease rapidly and a novel peak emerged at about
400 nm, the fluorescence intensity of peak located at about
470 nm is reduced to half of its original and the novel peak
increased obviously when radiated time reach to four hours.
DTBC-DPK film exhibit strong sensitivity to light irradiation,
after twenty minutes, the luminescence peak of DTBC-DPK film
appeared blue shift, and the fluorescence intensity declined
radically. TTBC-TPE films show similar fluorescence emitting
behaviour to DTBC-TPE films because of their molecular
structure are analogous, the fluorescence intensity of DTBC-
TPE decayed when radiated for two hours with artificial
sunlight, but fluorescence of TTBC-TPE film receded until
radiated time reach to three hours. It indicates that TTBC-TPE
film is more stable than DTBC-TPE film which probably due to
the bigger periphery substitutions of TPE in TTBC-TPE, which is
more effective to inhibit rotation of molecular bonds. The
above four light convention films all suffered some degree of
fluorescence decay in artificial sunlight condition, however,
TPA film display excellent photo stability even if in long
irradiation time which was reach to four hours. Then, the
fluorescence spectra of them in aggregated state are also
investigated in detail, the solid nano-particle of five
compounds could suspended evenly in THF/water mixture. As
shown in Fig. S2 and Fig.S4, the fluorescence spectra of TPE,
DTBC-DPK, TTBC-TPE and DTBC-TPE all shows time-dependent
degradation trend, and degradation rate is faster than in PVC
films. Fluorescence intensity of TPE and DTBC-TPE reduced by
around eighty percent and seventy percent, respectively, after
radiated with artificial sunlight for an hour and a half. For
TTBC-TPE and DTBC-TPE, their fluorescence intensity began to
reduce obviously after radiated for twenty minutes and almost
depleted when radiated time reach to an hour and a half.
Pleasantly, TPA still exhibit remarkable photo stability. But an
abnormal phenomenon occurred in its fluorescence spectra,
where the fluorescence intensity did not decrease but enhance
Fig. 4 The particle distribution of TPA in as-prepared mixture
(a) and after photo irradiation (b).
after photo irradiation. To explain this abnormal phenomenon,
the same experiments are repeated, but the same result is
obtained. According to some related literature home and
abroad, some AIE-active compounds show morphology-
dependent fluorescence, thus, we inferred that the abnormal
phenomenon results from the change of aggregation
morphology of suspended particle in the THF/water mixture.
In the course of the above experiments, some particle visible
to the naked eye have formed which did not exist in as-
prepared mixture. To further confirm that, the particle size of
as-prepared mixture and photo radiated mixture are tested by
zeta/nano particle analyzer. As shown in Fig. 4, the particle size
distribution of TPA in as–prepared mixture was mainly range
from 100 nm to 1000nm, and calculated particle average size is
427 nm, four types of different size of particle formed in photo
irradiated mixture, the calculated average size are 10 nm, 176
nm, 1348 nm and 29992 nm, respectively. Indeed, the particle
size of the as-prepared mixture has changed after photo
irradiation, which indicated that particle size of TPA could
affect the fluorescence intensity. In addition, to further
investigate the anti-photo degradation ability of them, we
have carried out oxidation reaction of them with 2,3-dichloro-
5,6-dicyano-1,4- benzoquinone(DDQ). The results show that all
of them could be oxidized by DDQ to varying degrees
(oxidation products of TTBC-TPE, DTBC-TPE and DTBC-DPK can
be detected by TLC, and the yields of TTBC-TPE and DTBC-TPE
are very low) except TPA. Zhu et al62 had reported previously
that TPE could be oxidized and generated DPP. Hence, it is a
better way to estimate and judge the stability of TPA by the
Fig. 5 UV-visible transmittance spectra of TPE, TPA, DTBC-DPK,
TTBC-TPE, DTBC-TPE in PVC films and blank PVC film.
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TTBC-TPE
DTBC-TPE
30.41/28.39
38.86/33.55
04.96/18.50
17.54/11.02
0.032
0.034
Compatibility and dispersibility of light conversion films
We utilized fluorescence microscopy to evaluate the
compatibility and dispersibility of luminogens in light
conversion films, the fluorescence microscopy photos shown
in Fig. 6. The blank PVC film has no fluorescence, only give a
dark image, other five light conversion films show obvious blue
fluorescence in different extent. In addition, we could find that
some bright unformed particles homogeneously dispersed in
PVC films. The fluorescence images illustrated that these light
conversion films possess good dispersibility and compatibility.
Mechanical property
Fig. 6 Fluorescence microscopy photos of blank PVC (a), and
TPE (b), TPA (c), DTBC-DPK(d), TTBC-TPE (e), DTBC-TPE (f) in
PVC films under UV-irradiation.
We referred the national standards of People's Republic of
China (GB/13022-91) employed the mechanical strength
testing of light conversion films. The stretching speed is setted
as 2mm/min. The thickness of light conversion films are tested
by millesima thickness gauge/AICE. All data are summarized in
Table 3. The thickness data is average value which calculated
by five random test point of light conversion film. From the
data we known that the tensile stress of dispersed light
conversion agents films are increased compared to the blank
PVC film, especially, TPA film increased near 2 folds. The
elongation also have changed to some extent after doped the
light conversion agents in the PVC film, DTBC-DPK film suffered
significantly impact which indicated it is very brittle, elongation
of TTBC-DPK film and DTBC-TPE film are also decreased. But,
elongation of TPE film and TPA film are increased intensively,
indicated they have excellent elasticity.
electron density of benzene rings. As electron withdrawing
group, acrylonitrile unit of TPA was able to reduce electronic
cloud of benzene rings, which caused TPA could not degrade
whether treated by photo irradiation or chemical reaction.
UV-visible transmittance analysis of light conversion films
Transmittance is one of the important properties of light
convention films, in addition, it is known that the doping of
light conversion agent could affect the transmittance to some
extent, so it is necessary to observe and study the
transmittance spectra of light conversion films. As shown in
Fig. 5, detail data are calculated by integrated area of
transmittance curve and summarized in Table 2. The
ultraviolet (200nm-380nm) transmittance are vary from TPE to
DTBC-TPE, among them, TPA give a very low transmittance in
ultraviolet region which is as lower as 6.83%, the
transmittance of other four light conversion films in ultraviolet
region are higher than TPA film except DTBC-DPK. Whereas,
ultraviolet light almost entirely penetrated through the blank
PVC film. It suggest that ultraviolet light could be shielded
effectively by these light conversion agents. The visible light
(400nm-700nm) transmittance of these light conversion films
are hold ca. 85%, and reduced compare to the blank PVC film
but only have a tiny change, which indicated that the doping of
light conversion agents only faintly affect the visible light
transmittance of PVC film. The excellent transmittance of
these light conversion film are ascribe to the good
compatibility and dispersibility of luminogens which will
mentioned below.
Experimental
Measurement and characterization.
1H NMR spectra and 13C NMR spectra were obtained with a
Varian inova instrument at 400 MHz and 100 MHz using
tetramethylsilane (TMS) as the internal standard, and CDCl3 as
the solvent in all cases. The UV-vis absorption spectra were
obtained on
a MaPada UV-3200PCS spectrophotometer.
Fluorescent emission spectra were obtained on a Hitachi F-
2500 fluorescence spectrophotometer. MALDI/HRMS was
record on an UltrafleXtreme MALDI-TOF/TOF mass
spectrometer (Bruker, Germany). Digital photographs were
taken by Canon 550D (Canon, Japan) digital cameras.
Fluorescence microscopy photos were obtained on OLYMPUS
BX53.
Table 2. Light transmittance of light conversion films.
Entry UV light (200nm-380nm) Visible light (400nm-
700nm)
Materials.
THF and CH2Cl2 were dried according to standardized
procedures previously described. All the other chemicals and
reagents used in this study were of analytical grade without
further purification. In general, all the intermediates and final
compounds were purified by column chromatography on silica
gel (200-300 mesh), and crystallization from analytical grade
solvents. Reactions were monitored by using thin layer
chromatography (TLC).
PVC
TPE
TPA
72.90%
15.98%
6.83%
88.44%
85.97%
84.65
DTBC-DPK
TTBC-TPE
DTBC-TPE
3.58%
13.81%
10.09%
80.95%
85.10%
84.53%
Synthesis.
Table 3. Mechanical property of light conversion films.
The molecules structure for TPE, TPA, DTBC-TPE, TTBC-TPE and
DTBC-DPK are shown in Scheme 1. TPE and TPA were
synthesized according to the McMurry coupling reaction; for
DTBC-TPE, TTBC-TPE and DTBC-PM, t-butyl-carbazole (TBC)
was introduced at first, then, McMurry coupling reaction
occurred with Benzophenone, to thus give final molecules; The
target molecules were characterized by 1H NMR, 13C NMR,
MALDITOF mass spectrometry.
Entry
Thickness(mm)
Tensile stress (Mpa)
Elongation (%)
Transverse/Portrait Transverse/Portrait
PVC
TPE
TPA
DTBC-DPK
24.63/25.55
41.03/40.07
45.08/45.58
33.03/32.54
19.26/15.62
11.72/47.68
41.09/67.17
03.77/05.01
0.054
0.034
0.062
0.076
4 | J. Name., 2012, 00, 1-3
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Preparation of 2,3,3-triphenylacrylonitrile (TPA)
was purified by column chromatography (silica gel, CH2Cl2–
In a dual-neck flask diphenyl ketone (5.8 g, 22.3 mmol) and petroleum ether). Yield: 52%; 1H NMR (400 MHz, CDCl3) δ/ppm
sodium cyanide (1.1 g, 60%) are dissolved into 30 mL = 8.14 (d,J=1.6 4H), 7.48 (dd,J1=2.0,J2=8.4, 4H), 7.39-7.34 (m,
12H), 7.24-7.16 (m, 10H), 1.49 (s, 36H) (Fig. S11); 13C NMR (100
anhydrous toluene, stirred 30min at 90
℃ under argon
MHz, CDCl3): δ/ppm = 143.53, 142.96, 142.56, 142.15, 139.65,
139.26, 136.62, 132.81, 131.57, 127.98, 127.01, 126.02, 123.70,
123.50, 116.34, 109.41, 34.89, 32.18 (Fig. S12). HRMS (MALDI-
TOF): m/z 886.5201, calculated 886.5221 (Fig. S18).
Preparation of 1,1,2,2-tetrakis(4-(3,6-di-tert-butyl-9H-carbazol-9-
yl)phenyl)ethane (TTBC-TPE).
This compound was prepared by following the synthetic
procedure described for TPE using bis(4-(3,6-di-tert-butyl-9H-
carbazol-9-yl)phenyl)methanone. The crude product was
atmosphere, then benzene acetonitrile (4.7 g, 23.5 mmol) in
20 mL anhydrous toluene solution was slowly added drop wise
in 1 h. The reaction mixture was reacted for 10 h at 90℃.
Upon cooling, the mixture was poured into 100 mL ice water,
and washed by saturated sodium chloride solution three times.
Then, extracted with CH2Cl2. The combined organic layers were
dried over anhydrous Na2SO4 and evaporated in vacuum. The
crude product was purified by chromatography (silica gel,
CH2Cl2/petroleum ether). Yellowish solid was obtained. Yield:
42%; 1HNMR (400 MHz, CDCl3) δ/ppm = 7.45-7.42 (m, 5H)
7.26-7.17 (m, 8H), 7.01-6.99 (m, 2H) (Fig. S8); 13C NMR (100
MHz, CDCl3): δ/ppm = 157.79, 140.44, 139.08, 130.81, 129.95,
129.90, 129.74, 129.02, 128.52, 128.49, 128.39, 128.27(Fig. S9).
HRMS (MALDI-TOF): m/z 282.0 calculated 281.1 (Fig. S16).
Preparation of 1,1,2,2-tetraphenylethene (TPE)
purified
by
column
chromatography
(silica
gel,
CH2Cl2/petroleum ether). Yield: 50%; 1H NMR (400 MHz, CDCl3)
δ/ppm = 8.14 (s, 8H), 7.52-7.47 (m, 16H), 7.40 (d,J=0.8, 16H),
1.45 (s, 72H) (Fig. S13); 13C NMR (100 MHz, CDCl3): δ/ppm
=142.98
123.69
Preparation
，
141.65
123.49, 116.27
of
，
139.05
，
109.28
137.00
，
，
34.76， 32.06 (Fig. S14).
132.82
， 125.98,
，
，
bis(4-(3,6-di-tert-butyl-9H-carbazol-9-
yl)phenyl)methanone (DTBC-DPK).
In an oven-dried dual-necked flask equipped with a stir-
magneton, diphenyl ketone (1.44g, 8.0mmol) and zinc powder
(2.08g, 32mmol) were combined. A balloon filled with argon
was connected to the dual-necked flask via the side tube and
In a dual-neck flask 3,6-di-tert-butyl-9H-carbazole (TBC) (5.58
g, 20 mmol) and potassium tert-butoxide (3.37 g 30 mmol) are
dissolved into 30 mL anhydrous DMF, then bis(4-fluorophenyl)
methanone (2.18 g, 10 mmol) in 30 mL anhydrous DMF
solution was slowly added drop wise in 1 h under a argon
atmosphere. The reaction mixture was reacted for 10 h at 110
purged for 3 times
tube via a double needle at vacuum condition, and move on to
a cryostat stir 10 min at -78 . At last, titanium tetrachloride
，Then dried THF (50mL) was added to the
℃
℃
. Upon cooling, the mixture was poured into 200 mL ice
(1.73ml, 16mmol) was added via syringe, stir 30min
sequentially, after that move out them from the cryostat and
cool down to room temperature naturally. The dual-necked
water, then a deep yellow solid precipitate was filtered off and
washed with ethanol. After vacuum drying the crude product
and purified by chromatography (silica gel, CH2Cl2/petroleum
ether). 5.16 g of yellow solid was obtained. Yield: 70%. 1HNMR
(400 MHz, CDCl3) δ/ppm = 8.15 (d,J=8.0, 8H), 7.78 (d,J=8.0,
4H), 7.50 (d,J=1.2, 8H), 1.48 (s, 36H) (Fig. S15); HRMS (MALDI-
TOF): m/z 736.3, calculated 736.4 (Fig. S17).
was heated at 80
℃ for 24 hours and then cooled to room
temperature. The reaction was quenched by water and added
K2CO3 (10%) solution. Then, extracted with CHCl3 three times.
The combined organic layers were dried over anhydrous
Na2SO4 and evaporated in vacuum. The desired products were
obtained. Yield 70%, after purification by flash
chromatography on silica gel with petroleum ether/ethyl
acetate, v/v =20/1.
Preparation of light conversion films.
In an oven-dried flask equipped with a mechanical stirrer
polyvinyl chloride (PVC) (4.95g) and TPA (0.05g) were dissolved
into 30 mL THF. The mixture was stirred for 12 h at room
temperature. After that, placed the flask into a ultrasonic
oscillators for 30 min to remove the bubbles of the mixture.
Then the mixture was poured onto a prepared glass plate and
paved rapidly with a glass rod. Finally, put them into ventilated
cabinets until the THF was volatilized completely, obtained a
contents of TPA was 1% (mass fraction) light conversion film of
Preparation of (9,10-diphenylphenanthrene) (DPP)
.
A 0.1 M solution of tetraphenylethylene ( TPE ) in a 1:9 mixture
of methanesulfonic acid and dichloromethane (10 mL) was
reacted with 1 equiv of 2,3-dicyano-5,6-dichlorobenzoquinone
(DDQ) at ∼0 ℃, under an argon atmosphere, to afford a blue-
violet solution63 which turned brown during the course of 30
min. The resulting brown mixture was quenched by added
saturated aqueous sodium bicarbonate solution (20 mL). The
dichloromethane layer was separated and washed with a
saturated brine solution (2×10 mL), dried over anhydrous
Na2SO4, and evaporated to afford the corresponding DPP in
quantitative yield.1H NMR (400 MHz, CDCl3) δ/ppm = 8.85
(d,J=8.4, 2H), 7.72-7.68 (m, 2H), 7.59 (dd,J1=4.0, J2=8.0, 2H),
7.54-7.50 (m, 2H), 7.27-7.18 (m, 10H) (Fig. S10).
Preparation
of
9,9'-((2,2-diphenylethene-1,1-diyl)bis(4,1-
phenylene)) bis(3,6-di-tert-butyl-9H-carbazole) (DTBC-TPE).
Scheme 1. Molecular structure of light conversion agents.
TPA. The light conversion films of TPE, DTBC-TPE, TTBC-TPE,
DTBC-DBK was prepared by the same procedure describe for
TPA, obtain final films of them with 1% mass fraction.
The compound was synthesized by the same procedure
described for TPE using bis(4-(3,6-di-tert-butyl-9H-carbazol-9-
yl)phenyl)methanone and diphenyl ketone. The crude product
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DOI: 10.1039/C6TC04215E
ARTICLE
Journal Name
Photodegradation of compounds in PVC films and aggregate state. 9.
K. Kim, G. Kim, B. R. Lee, S. Ji, S. Y. Kim, B. W. An, M. H.
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Photodegradation experiments was carried out by a 300W
10.
xenon lamp equipped with a filter which providing artificial
sunlight about 10 cm away from the aqueous solution and
sample of PVC films containing all compounds. The aqueous
suspensions containing all necessary compounds (in the THF–
H2O mixtures, where compounds could easily dissolve in THF,
and water was used because it is a non-solvent, the molecules
must aggregate in the aqueous mixtures) were put in a custom
quartz container which could not absorbed light irradiation.
11.
12.
13.
14.
15.
16.
17.
Conclusions
In summary, we have explored a new type of light conversion
film based on AIEgens, obtain a potential light conversion
agent via screen several typical AIEgens. Light conversion film
of TPA not only could effectively convert ultraviolet light
(200nm-380nm) into blue light (the maximum emission
wavelength was 430nm), but also possess excellent photo and
chemical stability. Their mechanical property and
transmittance were investigated in detail, result show that the
addition of AIEgens could not decreased the mechanical
property of PVC film except DTBC-DPK film, and the visible
light (400nm-700nm) transmittance of these light conversion
films are hold ca. 85%. In addition, these light conversion films
possess good dispersibility and compatibility. This work
furnishes a promising platform for the agricultural light
conversion area, and has advantage of cost compare to
traditional rare metal contained light conversion films.
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26.
This work was financially supported by the National Natural
Science Foundation of China (No. 21566034), National
University students' innovative pilot projects (201510759022),
the Key Programs for Science and Technology Development of
Shihezi University (GXJS2013-ZDGG02, 2014zrkxyq05).
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