Exploration of highly efficient light conversion agents for agricultural film based on the bay-substituted perylene diimides derivatives

Article abstract of DOI:10.1016/j.dyepig.2018.07.015

To explore highly efficient yellow-green light conversion agents used for agricultural film, six bay-substituted perylene diimides and their polyvinyl chloride doped films (by 0.5% weight addition) were prepared. The maximum absorption and emission peaks

Full text of DOI:10.1016/j.dyepig.2018.07.015

Accepted Manuscript
Exploration of highly efficient light conversion agents for agricultural film based on the
bay-substituted perylene diimides derivatives
Yongjiang Yu, Yongtao Wang, Wenjing Liu, Xin Jia, Lei Ma, Litong Ren, Mei Xue,
Xiaohong Liu
PII:
S0143-7208(18)31091-X
10.1016/j.dyepig.2018.07.015
DYPI 6869
DOI:
Reference:
To appear in: Dyes and Pigments
Received Date: 14 May 2018
Revised Date: 12 June 2018
Accepted Date: 5 July 2018
Please cite this article as: Yu Y, Wang Y, Liu W, Jia X, Ma L, Ren L, Xue M, Liu X, Exploration of highly
efficient light conversion agents for agricultural film based on the bay-substituted perylene diimides
derivatives, Dyes and Pigments (2018), doi: 10.1016/j.dyepig.2018.07.015.
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ACCEPTED MANUSCRIPT
Exploration of highly efficient light conversion agents for
agricultural film based on the bay-substituted perylene diimides
derivatives
Yongjiang Yu a, Yongtao Wang* ac, Wenjing Liu a, Xin Jia* a, Lei Ma* b, Litong
Ren a, Mei Xue aand Xiaohong Liu a
aSchool of Chemistry and Chemical Engineering/Key Laboratory for Green Processing of
Chemical Engineering of Xinjiang Bingtuan，Shihezi University，Shihezi 832003, P. R. China
bTianjin International Center for Nanoparticles and Nanosystem, Tianjin University, Tianjin,
300072, P. R. China.
cShenyang University of Chemical Technology
*Author for correspondence: wyt_shzu@163.com; jiaxin@shzu.edu.cn; lei.ma@tju.edu.cn

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Abstract
To explore highly efficient yellow-green light conversion agents used for agricultural film, six
bay-substituted perylene diimides and their polyvinyl chloride doped films (by 0.5% weight
addition) were prepared. The maximum absorption and emission peaks of the luminogens-doped
polyvinyl chloride films are located at 581-609nm and 647-667nm, respectively. More importantly,
the fluorescence quantum yields of PTCDA, t-BuOPTCDA and m-MeOPTCDA are up to 0.88,
0.84 and 0.78 in doping film, respectively. The strengthening solar radiation and outdoor exposure
to sunlight last 160 minutes and two months respectively and the emission intensity of
m-MeOPTCDA-doped film displays slight changes and 9 percentage fluctuation in turn.
Combined transmittance, compatibility, mechanical properties and thermal stability,
m-MeOPTCDA is chosen as the best effective light conversion materials. To better understand the
optical properties of the luminogens, molecular configuration optimization, electron cloud density
distribution and molecular orbital energy levels were completed by theoretical calculation. Further,
the double layer coextrusion film containing m-MeOPTCDA and Triphenyl acrylonitrile is
succeed in dual band excitation（350 nm and 580 nm）and emission (430 nm and 651 nm), by
optimizing the proportion of m-MeOPTCDA and Triphenyl acrylonitrile, the special light
conversion films for different crops will be expected.
Keywords: photosynthesis, fluorescence, light conversion film, light conversion agents, perylene
diimides.
1
Introduction
The non-renewable energy such as coal, oil and natural gas is in the danger of drying
up. As a clean and renewable energy, the solar energy has been one of the research
focal points of the modern agricultural science and technology [1-4]. It is well known
that photosynthesis plays the most critical role in plant growth, and photosynthesis of
plants heavily rely on pigments of leaves, such as chlorophyll a, b and β carotene. By
absorbing the blue-violet band (400–480 nm) and red-orange band (600–700 nm) of
the sunlight, the pigments conduct photosynthesis of plants[5-8]. By converting the
ultraviolet (280–380 nm) light and yellow-green light (510–580 nm) of sunlight into
the plant photosynthesis needs blue-violet light (400–480 nm) and red-orange light
(600–700 nm), the agricultural shed film with addition of light conversion agents can
improve the yield and quality of crops[9-11]. However, most of the existing light
conversion agents only can convert ultraviolet light, the yellow-green light conversion

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agents are not only rarely, but they are also unstable[12]. In addition, the content of
ultraviolet light is only equivalent to 1%-2% of yellow-green light of the solar
spectrum. Therefore, converting only 5% yellow-green can outweigh the conversion
effect of whole ultraviolet light. Based on the above background, it can be deduced
that it is an urgent task to explore highly efficient yellow-green light agents.
The highly efficient yellow-green light conversion agents should possess high
luminescence efficiencies, excellent thermal stability, resin compatibility, weather
resistance, low cost and fluorescence emission matching with crops absorption spectra.
In order to guarantee the matched spectrum, the absorption spectrum of yellow-green
light conversion agents should be located in the region of 510-580 nm, and the
fluorescence emission peak should be near 650 nm. Obviously, the luminogens with
the above characteristics are difficult to obtain. According to the literature reports,
perylene diimides (PDI) have rigid planar conjugated structure, outstanding light
resistance, chemical and thermal stability[13, 14], but the planar molecular
configuration makes the PDI to easily form π-π packing in the solid state or doped
film, leading to the fluorescence quenching[15]. In addition, PDI also suffer notorious
self-absorption and solubility problems. To solve the above problem, a series of
bay-substituted PDI derivatives has been designed and synthesized by Pd(0)-catalysed
Suzuki cross-coupling or nucleophilic substitution reaction[16, 17]. For comparison,
the 1,6, 1,7 and 1,6,7,12, bay-substituted PDI derivatives (Figure 1) show enhanced
solid state fluorescence efficiency and solubility due to twisted molecular
conformation[18-22]. Recently, the PDI derivatives have extended their applications
Figure 1 Perylene diimides with position numbers.

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into organic photovoltaic devices[23-25], piezochromic switching[26], biological
probes[27],
bio-labelling[28],
near-infrared
fluorescence
materials[29],
transistors[30-32], light emitting diodes[33-34], luminescent solar concentrators[35]
and so forth. However, as light conversion materials for agricultural film, the
application and evaluation of bay-substituted PDI derivatives are rarely available in
the literature until now.
To obtain highly efficient yellow-green light conversion agents, in this work, six
different bay-substituted PDI derivatives, named PTCDA, o-MePTCDA,
m-MeOPTCDA, p-MeOPTCDA, m-2MeOPTCDA, and t-BuOPTCDA, have been
synthesized (As shown in Scheme 1). By the tests of photophysical properties and
theoretical calculation, the structure-photophysical property relationships of the light
conversion agents are analyzed and discussed in detail. Finally, the results show
coextrusion film successfully achieved blue-violet (430 nm) and red-orange light (651
nm) emission, and the optimum excitation wavelength are located in ultraviolet and
yellow-green light region. More importantly, the special film for different crops is
expected to be completed by tuning adding proportion between PDI derivatives and
Triphenylacrylonitrile(TPA).
Scheme 1 Synthetic routes of PTCDA, m-2MeOPTCDA, t-BuOPTCDA, p-MeOPTCDA,
o-MeOPTCDA and m-MeOPTCDA
2
Experimental Details
2.1 Measurements and characterizations

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The UV-vis spectra were determined on a Mapada UV-3200pcs spectrophotometer.
Fluorescence measurements were taken on Agilent Cary Eclipse fluorescence
spectrophotometer. 1H NMR and 13C NMR spectra were obtained with a Varian inova
instrument at 400 MHz and 100 MHz using tetramethylsiane (TMS) as the internal
standard, and CDCl3 as the solvent in all cases. MALDI/FIRMS were recorded on an
Ultrafle Xtreme MALDI-TOF/TOF mass spectrometer (Bruker, Germany).
Fluorescence microscopy images were obtained on OLYMPUS BX53.
Photodegradation experiments were carried out by a 300W xenon lamp equipped with
a filter, and radiation intensity of artificial sunlight is up to 129 mW/cm2. Thermal
stability was determined by thermogravimetric analyzer (TGA, Netzsch STA449F3)
over a temperature range of 40-1000
at a heating rate of 20 /min under N2
atmosphere. The fluorescence quantum yields of PDI luminogens CHCl3 solution
were determined by the comparative method using t-BuOPTCDA (Φf = 0.72 in CHCl3)
as reference[36]
2.2 Materials and Synthesis
THF, DMF and toluene were dried according to standardized procedures previously
described. The synthetic method of the PBI-Cl and TPA was carried out according to
the reported literature[3, 37]. 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) while the reactions were monitored by thin-layer chromatography (TLC).
Synthesis
of
bis(2,6-diisopropylphenyl)-5,6,12,13-tetraphenoxyanthra[2,1,9-def:6,5,10-d'e'f']diisoq
uinoline-1,3,8,10(2H, 9H)-tetraone(PTCDA): PBI-Cl (1.7 g, 2 mmol) was stirred
under argon with phenol (1.6 mL, 16 mmol) in N-methyl-pyrrolidone (60 mL) in a
250 mL round flask in the presence of powdered anhydrous K2CO3 (1.1 g, 8 mmol).
The temperature was maintained at 90 overnight under N2. After cooling to room

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temperature, the reaction liquid was poured into the water and extracted with ethyl
acetate. The combined organic layers were dried over anhydrous Na2SO4 and
evaporated in vacuum. The crude product was purified by chromatography (silica gel,
1
ethyl acetate: petroleum=1:10). Red solid was obtained. Yield: 92%. H NMR (400
MHz, ) δ 8.26（s, 4H）, 7.50 – 7.38 (t, 2H), 7.32 – 7.26 (m, 6H), 7.24 (d, J = 2.6 Hz,
6H), 7.09 (t, J = 7.4 Hz, 4H), 7.02 – 6.91 (m, 8H), 2.78 – 2.61 (m, 4H), 1.11 (d, J =
13
6.8 Hz, 24H) (Figure S6). C NMR (101 MHz, CDCl3) δ 163.17, 155.82, 155.28,
145.60, 133.17, 130.57, 129.99, 129.45, 124.59, 123.90, 122.91, 120.81, 120.39,
119.83, 29.10, 24.02 (Figure S12). LRMS (MALDI-TOF): m/z 1078.3 calculated
1078.4 (Figure S18).
Synthesis of 2,9-bis(2,6-diisopropylphenyl)-5,6,12,13-tetrakis(3,5-dimethoxyphenoxy)
anthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraone(m-2MeOPTCD
A): The compound was synthesized by the same procedure described for PTCDA
using 3, 5-dimethoxyphenol and PBI-Cl, The crude product was purified by
chromatography (silica gel, ethyl acetate: petroleum=1:10). Red solid was obtained.
1
Yield: 82%. H NMR (400 MHz, Chloroform-d) δ/ppm = 8.35 (s, 4H), 7.49-7.40 (m,
2H), 7.30 (d, J = 7.8 Hz, 4H), 6.24 (t, J = 2.2 Hz, 4H), 6.17 (d, J = 2.2 Hz, 8H), 3.66 (s,
24H), 2.72 (p, J = 6.8 Hz, 4H), 1.14 (d, J = 6.8 Hz, 24H). (Figure S7). 13C NMR (100
MHz, CDCl3): δ/ppm= 163.13, 161.62, 157.10, 155.32, 145.62, 133.02, 130.55,
129.49, 123.92, 122.98, 121.08, 120.78, 120.59, 98.48, 97.17, 55.40, 29.10, 24.00
(Figure S13). HRMS (MALDI-TOF): m/z 1318.5040 calculated 1318.5038 (Figure
S19).
Synthesis of 5,6,12,13-tetrakis(4-(tert-butyl)phenoxy)-2,9-bis(2,6-diisopropylphenyl)
anthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraone(t-BuOPTCDA):
The compound was synthesized by the same procedure described for PTCDA using
PBI-Cl and 4-(tert-butyl)phenol. The crude product was purified by chromatography
(silica gel, ethyl acetate: petroleum=1:8). Red solid. Yield: 89%. 1H NMR (400 MHz,
Chloroform-d) δ/ppm= 8.29 (s, 4H), 7.42 (t, J = 7.8 Hz, 2H), 7.27-7.23 (m, 12H), 6.87

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(d, J = 8.5 Hz, 8H), 2.77-2.65 (m, 4H), 1.28 (s, 36H), 1.13 (d, J = 6.4 Hz, 24H)
13
(Figure S8). C NMR (101 MHz, CDCl3) δ 163.33, 155.90, 152.78, 147.33, 145.59,
133.22, 130.67, 129.37, 126.66, 123.86, 122.68, 120.75, 120.16, 119.19, 34.36, 31.44,
29.07, 24.02 (Figure S14). LRMS (MALDI-TOF): 1302.5 calculated 1302.7 (Figure
S20).
Synthesis of 2,9-bis(2,6-diisopropylphenyl)-5,6,12,13-tetrakis(4-methoxyphenoxy)
anthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraonep(p-MeOPTCD
A): The compound was synthesized by the same procedure described for PTCDA
using PBI-Cl and 4-methoxyphenol. The crude product was purified by
chromatography (silica gel, ethyl acetate: petroleum=1:10). Red solid. Yield: 86%. 1H
NMR (400 MHz, Chloroform-d) δ/ppm= 8.18 (s, 4H), 7.50 -7.38 (m, 2H), 7.28 (s,
4H), 7.00-6.91 (m, 8H), 6.89- 6.77 (m, 8H), 3.79 (s, 12H), 2.69 (p, J = 6.8 Hz, 4H),
1.12 (d, J = 6.8 Hz, 24H) (Figure S9). 13C NMR (101 MHz, CDCl3) δ 163.28, 156.66,
156.59, 148.49, 145.61, 133.18, 130.69, 129.37, 123.84, 122.69, 121.33, 120.17,
119.92, 119.30, 115.20, 55.71, 29.08, 24.03 (Figure S15). LRMS (MALDI-TOF):
1198.4 (Figure S21).
Synthesis of 2,9-bis(2, 6-diisopropylphenyl)-5,6,12,13-tetrakis(2-methoxyphenoxy)
anthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraone(o-MeOPTCDA
): The compound was synthesized by the same procedure described for PTCDA using
PBI-Cl and 4-(tert-butyl)phenol The crude product was purified by chromatography
(silica gel, ethyl acetate: petroleum=1:8). Red solid. Yield: 81%. 1H NMR (400 MHz,
Chloroform-d) δ/ppm= 8.10 (s, 4H), 7.44-7.37 (m, 2H), 7.27-7.25 (m, 4H), 7.11-7.03
(m, 8H), 6.90 (dd, J = 8.2, 1.2 Hz, 4H), 6.80 (td, J = 7.9, 1.4 Hz, 4H), 3.66 (s, 12H),
2.70 (p, J = 6.8 Hz, 4H), 1.12 (d, J = 6.8 Hz, 24H) (Figure S10). 13C NMR (101 MHz,
CDCl3) δ 163.56, 155.94, 151.13, 145.65, 143.22, 133.41, 130.90, 129.29, 125.74,
123.81, 122.35, 121.84, 121.16, 120.02, 120.00, 118.73, 112.50, 55.50, 29.08, 23.96
(Figure S16). LRMS (MALDI-TOF): 1198.4 (Figure S22)

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Synthesis of 2,9-bis(2,6-diisopropylphenyl)-5,6,12,13-tetrakis(3-methoxyphenoxy)
anthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraone(m-MeOPTCD
A): The compound was synthesized by the same procedure described for PTCDA
using PBI-Cl and 4-(tert-butyl)phenol The crude product was purified by
chromatography (silica gel, ethyl acetate: petroleum=1:10). Red solid. Yield: 85%. 1H
NMR (400 MHz, Chloroform-d) δ/ppm= 8.31 (s, 4H), 7.44 (t, J = 7.7 Hz, 2H), 7.29 (d,
J = 7.8 Hz, 4H), 7.19 (t, J = 8.2 Hz, 4H), 6.68 (dd, J = 8.3, 2.3 Hz, 4H), 6.61 (dd, J =
8.1, 2.1 Hz, 4H), 6.53 (t, J = 2.3 Hz, 4H), 3.67 (s, 12H), 2.72 (p, J = 6.9 Hz, 4H), 1.13
13
(d, J = 6.8 Hz, 24H) (Figure S11). C NMR (101 MHz, CDCl3) δ 163.15, 161.02,
156.38, 155.60, 145.61, 130.57, 130.38, 129.47, 123.91, 122.95, 120.75, 120.69,
120.47, 111.96, 110.72, 105.85, 55.36, 29.10, 24.02 (Figure S17). LRMS
(MALDI-TOF): 1198.4 (Figure S23)
2.3 Preparation of light conversion films
Polyvinyl chloride (PVC) (2.4725 g) and PTCDA (0.0125 g) were dissolved into 16
mL THF in a mechanical stirrer containing single drying flask. The mixture was
stirred for 12 h at room temperature and placed in the ultrasonic oscillator for 30
minutes to remove the bubbles from the mixture. The mixture was poured onto a glass
plate and paved rapidly with a glass rod. Finally, the mixture was placed into
ventilated cabinets until THF volatilized completely, and light conversion film of
PTCDA (0.5% mass fraction) was obtained in this way. The other light conversion
films were prepared according to the same method. The composite light conversion
films were prepared by tuning weight ratio of TPA (the weight ratio of TPA:
m-MeOPTCDA=1:1, 2:1 and 4:1, and maintain 0.5% weight ratio between PDI
derivatives and PVC).
3
Results and Discussion
3.1 Photo-physical properties in solutions and PVC film

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To analyze the impact of various bay position substituents, the UV-vis absorption
spectra and fluorescence emission spectra of six PDI derivatives have been
investigated in different polar solvents. As shown in Figure S1 and Table S1, in
addition to the ultraviolet region, the PDI dyes exhibit three absorption bands ranging
from 400 to 630 nm, the corresponding absorption peaks are located near 450, 540
and 570 nm, respectively. Furthermore, the broad peak at 450 nm and the shoulder
peak at 540 nm are assigned to the S0–S2 transition, while the strongest absorption
peak at 570 nm is related to the S0–S1 transition[38]. With the increase of solvent
polarity, the maximum absorption peak (TMAP) between toluene and THF shows
abnormal shift due to solvation effect of toluene, which leads to extended molecular
conjugation. Generally, TMAP of the PDI dyes only exhibits less than 10 nm shift
with the change of polarity of solvent, which shows that the polarity of solvent has
little influence on the ground state energy level. Compared with steric substituent
effects, the electron donating ability of substituents has notable influence on electron
delocalization. Taking p-MeOPTCDA as an example, the maximum absorption peak
shows the most obvious redshift in THF and DMF due to the stronger electron
donating ability of p-MeO group. Similar to absorption spectra, the maximum
fluorescence emission peak of the dyes also exhibit tiny shift (19 nm at most) with the
change of solvent polarity and substituent. To screen the best yellow-green light
conversion agent, the excitation and emission spectra of PVC films doped PDI dyes
are tested. As shown in Figure S2 and Table S2, the maximum excitation and
emission peak are located at 581-609 nm and 651-667 nm, respectively. Obviously,
larger stokes shifts are desirable for decreasing of re-absorption of emission, and the
red-shifted fluorescence emission peaks match well with the absorption spectrum of
crops in the region of red-orange light. Combined with the excitation spectra, PTCDA
and m-MeOPTCDA are the most appropriate yellow-green light conversion materials
in the PDI luminogens. The maximum excitation and emission peak of PTCDA and
m-MeOPTCDA are located at 581 nm and 651 nm, respectively. Although the
excitation peak of two dyes slightly exceeds the optimum region of 510-580 nm,
asymmetric curve of the excitation spectra is in favor of offsetting it. More interesting,

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PDI luminogens containing -OMe group show the smaller width of the half peak
(FWHM) than that of PTCDA and t-BuOPTCDA. Based on the preliminary study, the
bigger FWHF often means poor uniformity of crystal particles or amorphous states.
Thus, we speculate that the presence of -OMe group is beneficial to improve
crystallization properties of PDI dyes. To better understand the optical characteristics
of the PDI dyes, frontier molecular orbital analysis of the luminogens was performed
by using density functional theory (DFT) at the B3LYP/6-31G(d,p) level. As shown
in Figure 2, the electron clouds in both the highest occupied molecular orbital
(HOMO) level and the lowest unoccupied molecular orbital (LUMO) level are all
predominantly placed on the PDI unit, while only tiny amounts of HOMO

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Figure 2 B3LYP/6-31G(d,p) calculated molecular orbital amplitude plots of HOMO and
LUMO levels for PTCDA, o-MeOPTCDA, m-MeOPTCDA, p-MeOPTCDA,
m-2MeOPTCDA and t-BuOPTCDA.
levels extend to the bay-substituted aryl oxygen unit, indicative of faint intramolecular
charge transfer (ICT) characteristic in the molecules in accordance with spectroscopic
results. Compared with PTCDA, the HOMOs and LUMOs of the other
bay-substituted PDI compounds showed upshift more obviously due to the
electron-donating properties of –OCH3 and –OtC4H9 groups. However, the energy
gaps of PDI derivatives were irregular. In addition to increased MeOPTCDA, the
energy gaps of luminogens including o-MeOPTCDA, p-MeOPTCDA,
m-2MeOPTCDA and t-BuOPTCDA were smaller than PTCDA (Figure 2), which

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means that the alkoxy substituents with different type, position and amount can cause
varying degrees of change of the HOMOs and LUMOs. In addition to the
electron-donor ability of alkoxy groups, molecular conformation and packing also
affect optical characteristics of luminogens. Because of the stronger electron-donor
ability, the maximum excitation and emission peaks of p-MeOPTCDA and
t-BuOPTCDA are longer than that of the other compounds in the doping films, (Table
S2), while m-MeOPTCDA show blue-shifted maximum excitation and emission
peaks. Specially, m-2MeOPTCDA exhibited the shortest fluorescence emission peak
among the PDI dyes, which can be attributed to twisted PDI core and further
Figure 3 The fluorescence spectra of PDI luminogens in PVC films under sunlight for
different days
explanation will be given in the following section.
In order to investigate the photostability of light conversion agents, the test of
strengthening solar radiation is essential. Under strengthening solar radiation (129
mW/cm2), the fluorescence emission intensity of the doping films is evaluated at
different times. As shown in Figure S3, after 160 minutes, the fluorescence intensity
of o-MeOPTCDA and p-MeOPTCDA displays slight fluctuation, but, quite apart
from that, continuous radiation has almost no influence on the remaining PDI
luminogens. To further evaluate practical application performance of PDI luminogens,

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the fluorescent intensity of the doping films are investigated after outdoor exposure to
sunlight for two months. The o-MeOPTCDA film shows some minor differences, for
m-MeOPTCDA film, 91% of the initial intensity is reserved, and the shape and shift
of emission peaks are unchanged. As shown in Figure 3, the above results indicate
o-MeOPTCDA and m-MeOPTCDA have excellent weather resistance. However, the
initial fluorescence emission intensity of the luminogens are significantly different.
Among of them, fluorescence emission of p-MeOPTCDA is the weakest, while
PTCDA and m-MeOPTCDA exhibit the strongest fluorescence emission under
excitation of the same wavelength, which means PTCDA and m-MeOPTCDA may
have higher fluorescence quantum efficiency than the others. According to the
literature report[39], the aryloxy bay substituents and PDI core act as electron donator
and electron acceptor in bay-substituted PDI derivative, respectively, while
fluorescence quantum efficiency depend on ICT effect from electron donor to electron
acceptor. In addition, the ICT effect is related to the dihedral angles between the
aryloxy groups and the PDI core as well as the angle of the oxygen lone pair orbitals
relative to the π-orbitals of the PDI core. However, the opposite trends of the two
angles lead to irregularand unpredictable ICT effects. Different from the literature
reports, the PDI core is twisted into two naphthalimide planes A and B, and dihedral
angle of the two planes should be a significant influencing factors on ICT effects. For
comparison, PTCDA, m-MeOPTCDA and m-2MeOPTCDA have bigger dihedral
angle between plane A and B based on molecular structure optimization (As shown in
Figure 4), leading to diminished ICT effects and blue-shifted fluorescence emission.
Meanwhile, the twisted PDI core is conducive to decrease π-π stacking and improve
the solid-state fluorescence quantum efficiency, which is suitable for PTCDA and
m-MeOPTCDA possessing higher fluorescence quantum efficiency than the others,
but does nothing for explaining fluorescence quenching of m-2MeOPTCDA. In
general, the alkoxy substituents on benzene ring in bay position is not beneficial to the
improvement of solid-state fluorescence efficiency. In addition to ICT effect and
twisted PDI core, obtaining molecular arrangement and stacking mode may give a
better explanation. Next, we tried to cultivate single crystals of the compounds, but

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failed. Compared with the fluorescence quantum efficiency in solution and solid state,
the PVC doped films exhibit significantly enhanced fluorescence emission due to
doping and dilution effect,

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Figure 4 B3LYP/6-31G(d,p) calculated molecular structure of PTCDA(a),
o-MeOPTCDA(b), m-MeOPTCDA(c), p-MeOPTCDA(d), m-2MeOPTCDA(e) and
t-BuOPTCDA(f).
especially, fluorescence quantum yields of PTCDA, t-BuOPTCDA and
m-MeOPTCDA are up to 0.88, 0.84 and 0.78 respectively(Figure 5). Based on
theoretical calculation, t-BuOPTCDA has the best plane configuration generally
deteriorating the fluorescence properties of the solid state and doping films, so high
fluorescence quantum yields of t-BuOPTCDA should be attributed to the steric effect
of tert-butyl reducing intermolecular interactions. Obviously, the fluorescence
quantum yields of doping films cannot be simply sorted only by solid state quantum
yields of luminogens, for instance, t-BuOPTCDA. More importantly, the twisted

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degree of PDI core and large t-BuO group will provide theoretical guidance for
further molecular design of light conversion agents.
Figure 5 The Fluorescence quantum efficiency of PDI luminogens: a) solid state, b) in PVC films,
c) in solution (1x10-5mol/L, CHCl3), from left to right: PTCDA, m-2MeOPTCDA, t-BuOPTCDA,
p-MeOPTCDA, o-MeOPTCDA, m-MeOPTCDA. c) PVC films.
3.2 UV-visible transmittance analysis, compatibility and dispersibility of light
conversion films
Based on performance evaluation of light conversion agents, it is necessary to test the
transmittance curves of doping films. Taking PVC film as reference, the transmittance
of different wavebands is calculated by integrating the area of transmittance curve. As
shown in Figure 6 and Table S3, the transmittance curve indicates that there are
different degrees of decline in the whole UV-vis range. For the doping films, the
dominant light conversion regions are still yellow-green and ultraviolet lights.
Especially, only less than 30% yellow-green light can penetrate through the doping
films. Next to yellow-green light, the transmittance of ultraviolet light is lower than
50%. Compared to yellow green and ultraviolet light, the conversion of blue-violet
and red-orange light (600-650 nm) is not expected. Fortunately, PTCDA and
m-MeOPTCDA give about 90% transmittance in the region of 600-650 nm. Moreover,
the films doped with light conversion agents have almost no influence on
transmittance of the red-orange light (650–700 nm), which should be attributed to the
good compatibility and dispersibility between the PDI dyes and PVC matrix (Figure
5b).

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Figure 6 UV-visible transmittance spectra of PTCDA(a), t-BuOPTCDA(b),
o-MeOPTCDA(c), m-MeOPTCDA(d), p-MeOPTCDA(e) and m-2MeOPTCDA(f) in PVC
films and blank PVC film.
Mechanical properties of light conversion films
Referring to national standard (GB/13022-91), mechanical properties of the doping
films were tested at stretching speed of 10 mm min-1. Taking advantage of millesima
thickness gauge/AICE, the thickness of the light conversion films was tested and
calculated by averaging the testing values of five random test points. As shown in
Table 1, the data indicates that PTCDA film exhibits the worst tensile stress, but
apparent substitution effects are found in terms of tensile stress. Compared with PVC
film, tensile stress of the other doping films are improved by nearly 30%. Contrary to
tensile stress, it is difficult to find a clear regularity between the structure of PDI
luminogens and elongation. Among them, p-MeOPTCDA film exhibits the best
elasticity, followed by the PTCDA, m-2MeOPTCDA, m-MeOPTCDA,
o-MeOPTCDA and t-BuOPTCDA, while t-BuOPTCDA film suffers from a slight
decrease compare to PVC film. The large steric hindrance of t-Bu may be detrimental
to formation of intermolecular hydrogen interactions reducing elasticity of
t-BuOPTCDA.

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Table 1 Mechanical properties of light conversion films.
Tensile stress (Mpa)
Transverse/Portrait
33.13/31.20
Elongation (%)
Transverse/Portrait
13.50/12.49
Thickness
(mm)
Entry
PVC
PTCDA
0.053
0.050
0.053
0.054
0.047
0.056
0.050
24.03/24.03
44.23/48.52
42.07/41.87
43.53/49.89
38.55/47.94
43.27/48.58
40.12/41.09
33.71/33.20
11.53/11.37
101.97/88.05
20.09/13.01
m-2MeOPTCDA
t-BuOPTCDA
p-MeOPTCDA
o-MeOPTCDA
m-MeOPTCDA
57.11/19.90
3.3 Thermal stability
By the comparing the performance of the light conversion agents and their doping
films, PTCDA and m-MeOPTCDA have been appointed as the highly efficient
yellow-green light conversion agents. However, thermal stability of the light
conversion agents is an important evaluating indicator. As an ultimate showdown
between PTCDA and m-MeOPTCDA, thermal gravimetric analysis (TGA) are
observed. The thermal decomposition of PTCDA and m-MeOPTCDA can be divided
into two stages. The initial decomposition temperatures of PTCDA and
m-MeOPTCDA are 103 ˚C and 198 ˚C respectively, according to weight loss, the
bay-substituted benzene and MeO- may be removed in the first stage. In addition,
PTCDA shows a faster decomposition rate than m-MeOPTCDA, presenting as a tilted
line in the range of 100 ˚C. The second stages occur between 400 ˚C and 600 ˚C,
this rapid decomposition should be the result of decomposition, oxidation and
combustion. Generally, PTCDA and m-MeOPTCDA can meet the application
requirements of light conversion agents, but the higher initial decomposition
temperature and up to 493 ˚C Td (defined as the temperature at which a sample loses
its 5% weight) indicate that m-MeOPTCDA has excellent thermal stability (Figure 7).

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Figure 7 TGA thermograms of PTCDA(a) and m-MeOPTCDA(d)
recorded under nitrogen atmosphere at 10 ℃min-1 scan rates
The composite and the double layer coextrusion film containing m-MeOPTCDA
and TPA
Some crops prefer red-orange light compared with blue-violet light, but some crops
are just the opposite. Unfortunately, the excitation intensity scopes of m-MeOPTCDA
cover the blue-violet region. To reduce the adverse effect of blue-violet light
absorption as well as meet requirements of different crops, the tunable dual-band light
conversion films will become a development tend in the future. By tuning the adding
proportion of m-MeOPTCDA and TPA, the transmittance curves of composite films
are investigated. As shown in Figure S4 and Table S4, relative to the doping film of
single light conversion agent, the composite films obviously reduce transmittance of
ultraviolet light, and accompanied by increasing transmittance of blue-violet light and
yellow-green light. With the increasing of TPA, transmittance curve of the doping
film reveals tiny change in the blue-violet and the yellow-green region compared to
equal weight addition of TPA and m-MeOPTCDA. Compared with m-MeOPTCDA
film, fluorescence emission intensity of composite films reduced after the first
increase by UV light excitation. When the weight addition of m-MeOPTCDA and
TPA is 1:1 or 1:2, the enhanced red-orange light emission is obvious, however, the

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luminescence intensity decreases rapidly when the addition ratio of m-MeOPTCDA
and TPA is 1:4, which means that π-π interactions may occur. Unfortunately, the
fluorescence emission of all the composite films is almost imperceptible in the
blue-violet light region (As shown in Figure S5). Based on the above investigation, a
conclusion can be drawn that the addition of TPA may enhance emission intensity of
red orange light but do nothing to obtain dual band light conversion film, which is
attributed to Förster energy transfer from TPA to m-MeOPTCDA. To eliminate side
effects of the energy transfer, the double layer coextrusion film containing TPA and
m-MeOPTCDA layers is prepared. Meanwhile, taking m-MeOPTCDA layer as outer
layer avoids absorbing blue-violet light from TPA layer. As expected, the bilayer film
is succeed in dual band excitation and emission (As shown in Figure 8). In addition,
the special light conversion films for different crops are expected to be prepared by
Figure 8 The fluorescence spectra of double layer coextrusion (red line,
λex=350 nm) and m-MeOPTCDA film (black line, λex=550 nm)
changing addition ratio of different light conversion agents.
4
Conclusion
In summary, a series of yellow-green light conversion agents for agricultural film
based on bay-substituted PDI dyes were successfully prepared after two steps of
reaction. The PDI fluorophores suffer from aggregation induced fluorescence
quenching problem, but exhibit enhanced fluorescence emission properties in PVC

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doped film. Especially for PTCDA, t-BuOPTCDA and m-MeOPTCDA, the
fluorescence quantum yields are up to 0.88, 0.84 and 0.78 respectively. The excellent
fluorescence property is attributed to dilution effect and restrained vibration and
rotation coming from polymer matrix, decreasing intermolecular interaction by large
substituent groups and twisted PDI core. Meanwhile, m-MeOPTCDA shows
remarkable photo stability, and the fluorescence emission intensity of the doping film
displays slight changes by strengthening solar radiation (129 mW/cm2) for 160
minutes, and fluctuates within the range of 9 percentage after outdoor exposure to
sunlight for two months. The comprehensive evaluation of the doping film in terms of
such aspects as optical characteristics, mechanical properties and thermal stability
indicate m-MeOPTCDA is the best light conversion agent among of the PDI
luminogens. The light conversion film doped m-MeOPTCDA not only emit matched
fluorescence (651 nm) with absorption spectra of crops, but also maintain
transmittance of 45% ultraviolet light and 25% yellow-green at 0.5wt% compared to
the blank PVC film, which means ultraviolet light and yellow-green light can be
converted effectively by m-MeOPTCDA, the results indicate that m-MeOPTCDA has
practical application value as light conversion agent used for agricultural film. Based
on the optical properties of the composite and double layer coextrusion film
containing m-MeOPTCDA and TPA, the composite film cannot achieve dual band
emission due to energy transfer between m-MeOPTCDA and TPA, while blue-violet
and red-orange light emission can be detected simultaneously from the double layer
coextrusion film by ultraviolet excitation, meanwhile, single red-orange light
emission can be detected by yellow-green excitation, which will provide an effective
way to obtain the special light conversion films for different crops by tuning the
addition ratio of m-MeOPTCDA and TPA.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Grant
Nos. 21766030, 21566034 ，11774255), the key program of Natural Science

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Foundation of Tianjin (Grant Nos.17JCZDJC30100), the Seed Program of Tianjin
University (Grant Nos. 2017XZC-0090). This paper is completed under the guidance
of associate professor Yongtao Wang, and theoretical calculation are provided by
Professor Lei Ma.
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Supporting Information For: Exploration of highly efficient light
conversion agents for agricultural film based on the bay-substituted
perylene diimides derivatives
Yongjiang Yu a, Yongtao Wang* ac, Wenjing Liu a, Xin Jia* a, Lei Ma* b, Litong
Ren a, Mei Xue aand Xiaohong Liu a
aSchool of Chemistry and Chemical Engineering/Key Laboratory for Green Processing of
Chemical Engineering of Xinjiang Bingtuan, Shihezi University, Shihezi 832003, Xinjiang, P. R.
China.
bTianjin International Center of Nanoparticles and Nanosystem, Tianjin University, Tianjin,
300072, P. R. China.
cShenyang University of Chemical Technology
*Author for correspondence: wyt_shzu@163.com; jiaxin@shzu.edu.cn；
maleixinjiang@gmail.com

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Table S1. UV-vis absorption and fluorescence emission wavelength of six compounds
at different solvents.
Entry
λmaxa (nm)
573/567/575
571/566/573
579/575/581
586/567/586
584/581/585
575/567/575
λmaxb (nm)
601/598/608
605/609/615
613/599/617
613/599/617
609/605/615
601/600/608
FWHM (nm)
PTCDA
37.08/43.06/41.69
35.59/41.46/42.25
37.45/35.89/40.29
34.72/40.06/50.10
33.52/35.22/47.98
36.44/39.14/40.46
m-2MeOPTCDA
t-BuOPTCDA
p-MeOPTCDA
o-MeOPTCDA
m-MeOPTCDA
a The maximum absorption wavelength. b The maximum emission wavelength. c The peak width at
half height (FWHM) of maximum emission peaks in different solvents. (left: toluene, middle: THF,
right: DMF).
Table S2. The maximum excitation wavelength and fluorescence emission
wavelength of six light conversion films.
Entry
λexca (nm)
λemb (nm)
FWHMc (nm)
PTCDA
582
583
590
609
590
651
647
658
667
657
651
48.89
44.40
50.06
45.24
46.22
45.66
m-2MeOPTCDA
t-BuOPTCDA
p-MeOPTCDA
o-MeOPTCDA
m-MeOPTCDA
581
a
b
c
maximum excitation wavelength. maximum emission wavelength. the peak width at half
height (FWHM) of maximum emission peaks in PVC film.
Table S3. Light transmittance of light conversion films at different wavelength
ranges.
Entry
λ (200-400nm) λ (400-500nm) λ (500-600nm) λ (600-650nm)
PTCDA
47.00%
45.01%
46.06%
40.92%
45.48%
45.17%
58.93%
55.50%
57.12%
47.83%
56.84%
54.91%
27.22%
26.97%
29.07%
21.88%
23.52%
25.43%
89.13%
91.21%
29.07%
60.80%
75.92%
89.29%
m-2MeOPTCDA
t-BuOPTCDA
p-MeOPTCDA
o-MeOPTCDA
m-MeOPTCDA

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Table S4. Light transmittance of mixed light conversion films at different
wavelength ranges (the mass of m-MeOPTCDA:TPA=1:0, 1:1, 1:2, 1:4).
Entry
λ (200-400nm)
λ (400-500nm)
λ (500-600nm)
λ (600-650nm)
1:0
1:1
1:2
1:4
45.17%
21.74%
16.24%
11.94%
54. 91%
60.26%
60.13%
61.67%
25.43%
29.90%
30.35%
31.68%
89.29%
91.92%
91.67%
91.31%
Figure S1 UV-vis absorption and fluorescence emission spectra of PTCDA(a),
t-BuOPTCDA(b), o-MeOPTCDA(c), m-MeOPTCDA(d), p-MeOPTCDA(e)
and m-2MeOPTCDA(f) in different polar solvents (1×10-5 mol/L).

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Figure S2. The excitation and emission spectra of t-BuOPTCDA(a),
m-MeOPTCDA(b), PTCDA(c), p-MeOPTCDA(d), o-MeOPTCDA(e) and
m-2MeOPTCDA(f) in PVC doped films (0.5% addition concentration by weight).

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Figure S3 The fluorescence spectra of PTCDA(a), t-BuOPTCDA(b),
o-MeOPTCDA(c), m-MeOPTCDA(d), p-MeOPTCDA(e) and m-2MeOPTCDA(f) in
PVC films (0.5% addition concentration by weight) under artificial sunlight
irradiation at different times.