Fluorescence modulation of a pyrazolone dye in the solid state based on energy transfer

Article abstract of DOI:10.1039/c5nj01781e

A new pyrazolone dye was synthesized and its fluorescence modulation was achieved based on energy transfer. The prepared pyrazolone dye was combined with a photochromic pyrazolone to obtain a fluorescence photoswitching material (FPM), which exhibits stable and reversible fluorescence photoswitching properties in the solid state. Upon characterization of the samples through ¹H NMR, XRD, FT-IR, UV and fluorescence spectra, it was found that the photochromic pyrazolone and the pyrazolone dye integrally retained their inherent properties in the FPM. An investigation of the FPM revealed that the photoswitching response depended on the fluorescence dye species, the content of the fluorescence dye and the synthetic route of the FPM. The photoswitching mechanism of the FPM was studied in detail using FT-IR, UV and fluorescence spectroscopy. The results show that the photochromism of the photochromic pyrazolone plays an important role in the efficient energy transfer from the pyrazolone dye to the keto-form of the photochromic pyrazolone. The emission wavelength of the pyrazolone dye hardly induces a photochemical reaction of the photochromic pyrazolone in the FPM, which has the potential to be used as a non-destructive fluorescence readout of optical information. This study presents a simple and efficient alternative to covalent systems to obtain FPMs, and it may be applied in photoelectronic devices.

Full text of DOI:10.1039/c5nj01781e

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DynamicDAOIr:t1i0c.1l0e39L/Ci5nNkJs017►81E
New Journal of Chemistry
Page 1 ofJ7ournal Name
Cite this: DOI: 10.1039/c0xx00000x
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ARTICLE TYPE
Fluorescence Modulation of a Pyrazolones Dye in the Solid State
Based on Energy Transfer
Hu Liu, Ji-Xi Guo, Dian-Zeng Jia*, Ming-Xi Guo, Lang Liu, Dong-Ling Wu
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
New pyrazolones dye is synthesized and its fluorescence modulation is achieved based on energy transfer. The prepared pyrazolones dye
is combined with photochromic pyrazolones to obtain fluorescence photoswiching material (FPM), which exhibits stable and reversible
1
fluorescence photoswiching property in the solid state. Upon characterization of the samples by H NMR spectra, XRD, FT-IR, UV
spectrum and fluorescence spectrum, it was found that photochromic pyrazolones and pyrazolones dye integrallty retained the inherent
10 properties in the FPM, respectively. An investigation of FPM revealed that the photoswiching response depended on fluorescence dye
species, the content of fluorescence dye and the synthetic route of FPM. The photoswitching mechanism of FPM was studied in detail by
FT-IR, UV spectrum and fluorescence spectrum techniques. The results show that the photochromism of photochromic pyrazolones
plays an important role in the efficient energy transfer from pyrazolones dye to keto-form photochromic pyrazolones. The emission
wavelength of the pyrazolones dye hardly induces the photochemical reaction of photochromic pyrazolones in FPM, which has potential
15 to be used as non-destructive fluorescence readout of optical information. This study represents a simple and efficient alternative to the
covalent system to obtain FPM, and it may be applied in photoelectronic devices.
nanoparticles by grafting the fluorescent carbon nanoparticles
1. Introduction
with the copolymers of styrene and spiropyran, the fluorescent of
fluorescent carbon nanoparticles was modulated by the
copolymers of styrene and spiropyran.22 Diaz et al. devised
40 skillfully a photoswitchable semiconductor nanocrystals based on
energy transfer between the semiconductor core functions and
multiple photochromic diheteroarylethene groups.23 However,
among the photomodulatable compounds mentioned above, they
only show photoreaction property in solution, which limit their
45 applications in photoelectronic devices. In the large family of
photochromic material, the photochromic pyrazolones material
can exhibit excellent fatigue resistance, good thermal stability in
pure solid state. Therefore further works, which utilize
photochromic pyrazolones to modulate the fluorescent of
50 fluorescence dye, can exploit the excellent properties of
photochromic pyrazolones.24,18 We have successfully developed
the reversible fluorescence photoswitching system based on
doping inorganic fluorescence dye (Sr2P2O7-EC) into
photochromic pyrazolones.25 But there is differences in physical
Due to the non-invasive character, high selectivity and high
20 sensitivity of fluorescence detection, coupling fluorescence
molecule to photochromic units1-4 and doping fluorescence dye
into photochromic system5-8 are two attractive ways to develop
multifunctional FPM for optical memories,9-11 super resolution
imaging,12,13 and protein trafficking in living cells.14-16 To realize
25 fluorescence photoswitching, i.e., to modulate fluorescence
emission upon external light stimulus, photochemical reaction is
commonly the fundamental regulatory step. Photochromism, a
photoinduced reversible reaction between two isomers, is one of
the essentially photochemical reactions to facilitate the reversible
30 fluorescence photoswitching process in FPM.17,18 Various reports
have been published regarding reversibly photoswitchable
fluorescent molecules in recent years. Photochromic molecules,
such as diarylethene, spiropyran or azobenzene, are employed as
key units to toggle the fluorescence “on” and “off” repeatedly.19,21
35 For instance, Liao et al. constructed
a photoswitchable
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and chemical properties between inorganic fluorescence dye and
2. Experimental
2.1 Materials
40 1,3-Diphenyl-5-pyrazolone (DPP) was synthesized according to
the literatures.28 4-phenylsemicarbazide (PSC), 3-chlorobenzoyl
photochromic pyrazolones in this material, which may limit this
material to be applied in photoelectronic devices. Thus, utilizing
the similar structure of pyrazolones dye and photochromic
pyrazolones, we conceive another FPM by doping pyrazolones
dye into photochromic pyrazolones system.
5
chloride
and
3-chloro-2-fluoro-5-trifluoromethyl)-benzoyl
chloride were purchased from Aldrich Company USA. The other
materials were AR grade obtained from commercial sources and
45 used without further purification.
Fortunately, the as-synthesized pyrazolones dye shows strong
fluorescence emission and optical waveguide performance in the
solid state. So the developed FPM can be exploited for
10 photoswitches and optical waveguide devices.26,27 In this work,
we report a simple FPM in which pyrazolones dye is blended
with photochromic pyrazolones: 1,3-diphenyl-4-(3-chlorobenzal)
2.2 Instrument
1H NMR spectra were performed on an INOVA-400 NMR
spectrometer with DMSO-d6 as solvent. Melting point was
measured with a TECHXT-5 melting point apparatus. The
50 elemental analysis were made on FLASH EA 1112 Series
NCHS–O analyser. Absorption spectra were measured on Hitachi
UV-3010 spectrometer equipped with an integrating sphere
accessory. Fluorescence spectra were studied using a Hitachi
F-4500 fluorescence spectrophotometer (an optical filter was
55 used at the excitation window). FT-IR spectra were recorded by
using infrared diffuse reflectance spectroscopy in the range
400–4000 cm-1 on a BRUKER EQUINOX-55 spectrometer. A
ZF-1 ultraviolet analysis instrument equipped with an ultraviolet
lamp (15 W cm-2) as the light source was used to induce
60 photochromic reactions, the distance between the sample and the
light source was 15 cm.
-5-hydroxypyrazole-4-phenylsemicarbazone
(2a)
as
the
photochromic compound and 1,3-diphenyl-4-(3-chloro-2-
15 fluoro-5-trifluoromethyl)-5-pyrazolone (1) as the fluorescence
dye. The constructed FPM shows high efficiency and remarkable
fatigue-resistance in the solid state. Schematic illustration of this
photoswitchable system is shown in Scheme 1.
20 Scheme 1 Schematic illustration of energy transfer of FPM. After 365 nm light
irradiation, the fluorescence of 1 is quenched due to intermolecular energy
transfer from 1 to 2b.
2.3 Synthesis
The photochromic pyrazolone molecule is a modulator as an
energy acceptor of 1 to toggle fluorescence “on” and “off”
25 following with 365 nm light irradiation or heating. We choose 1
as a desirable compound to realize fluorescent toggling by
photochromic pyrazolones as photomodulator because of the
fluorescent emission band of 1 overlaps well with the absorption
spectrum of the keto-form isomer of photochromic pyrazolone
30 unit. This is an essential criterion for effective energy transfer
between the keto-form isomer of photochromic pyrazolone and 1.
In this case, the photoinduced switching of photochromic
pyrazolone unit converts from enol-form isomer to keto-form
isomer, which efficiently modulate the ON/OFF switching of
35 fluorescence emission of 1. Such an observation may provide an
alternate approach for designing and developing novel
optoelectronic materials.
2.3.1 Synthesis of pyrazolones dye
65
Scheme 2 Synthesis route of 1.
The intermediate 1,3-diphenyl-4-(3-chlorobenzal)-5-pyrazolone
(DP3ClBP) and 1,3-diphenyl-4-(3-chloro-2-fluoro-5-trifluoro-
methyl)-5-pyrazolone (1) were synthesized according to literature
(Scheme 2).24 For 1. Yield: 78%. Mp. 193.5-194.7 oC. MS:
70 m/zM+: 460.1. Elemental analysis: (C23H13ClF4N2O2): Calcd. (%)
C, 59.95; H, 2.84; N, 6.08. Found: (%) C, 59.65; H, 2.91; N, 6.12.
1H NMR (400 MHz, DMSO-d6): 8.80-8.75 (m, 1H), 8.57
(Substituted phenyl-ring, 2H), 8.47-6.92 (phenyl-ring, 10H).
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FT-IR (ν, cm-1): 3082 ν(O-H), 1673 ν(C=O), 1595, 1534
ν(phenyl), 1494, 1443 ν(pyrazole-ring) , 1250, 1050 ν(C-O).
2.3.2 Synthesis of photochromic pyrazolones compound
1,3-Diphenyl-4-(3-chlorobenzal)-5-hydroxypyrazole-4-phenyl-
5
semicarbazone (2a) was synthesized according to the literature.25
2.3.3 Synthesis of FPM
Several methods have been used to fabricate FPM: 1) When
photochromic pyrazolones is dissolved by the polar solvents, the
photochromic property of photochromic pyrazolones is easily
10 affected by solvation during the drying process. The constructed
FPM can’t exhibit reversible or even no photochromic property
(Fig. S2(C, D)), which is crucial for fluorescence modulation.
Unfortunately, there is not a suitable solvent which can allow
photochromic pyrazolones occur reversible photoisomerization
15 reaction in the solution. 2) After optimizing the experiment
conditions, the co-crystallization of 1 and 2a is a more suitable
method. Therefore, we designed and constructed successfully
FPM during the synthesis process of 2a by adding the compound
1 according to the literature of our previous work.25 After the
20 reaction and then cooling down to room temperature, white
powders were obtained from the solution and repeatedly purified
by ethanol at room temperature. The purified powders were
directly used for spectroscopic analyses. Different proportion of
FPM was successfully prepared by this way. Especially proposed,
25 1 can not react with 4-phenylsemicarbazide for its steric
hindrance effect, so FPM is only composed of 1 and 2a, which
was confirmed by XRD data (Fig. S1A). The concentration of 1
in FPM was calculated by 1H NMR data (Fig. S1(B-F)).
35 Fig. 1 (a) Absorption spectra changes of 2a under 365 nm light irradiation
(black line) and heating (red dash line), absorption spectra of 1 (blue line) in
the solid state. (b) Fluorescence emission spectra of 1, before (red dash line)
and after (black line) 365 nm light irradiation for 60 minutes in the solid state
(λex = 330 nm). (c) Fluorescence image of 1.
40 The absorption spectra of 2 and 1 were measured in the solid state,
respectively (Fig. 1a). The 2a transfers into 2b
(photoisomerization product of 2a) with 365 nm light irradiation,
and the absorption band intensity (350-470 nm) of 2b is
increasing by photoisomerization of 2a. The original absorption
o
45 spectrum of 2a is recovered completely by heating at 120 C in a
constant temperature oven. There was almost no absorption for 1
after 400 nm, which excludes the possibility of self absorption. In
addition, the fluorescence spectral of 1 is not affected by 365 nm
light irradiation, which indicates that 1 is photostable under 365
50 nm light irradiation (Fig. 1b). The fluorescence emission
spectrum of 1 centered at 417 nm (λex = 330 nm) and the
fluorescence image of 1 (Fig. 1c) show that 1 has intense
fluorescence. As shown in Fig. 1c, the microtopography of 1
is the rod-like structure, there are two luminescent spots in the
55 two endpoints of each rod, which indicates that 1 is an optical
waveguide material in pyrazolone derivatives. So developing
FPM may be helpful to exploit the application value of
3. Results and Discussion
30 3.1 Basic properties of the photochromic pyrazolones
and pyrazolones dye
pyrazolones
dye
and
photochromic
pyrazolones
in
photoelectronic devices.
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of FPM. When irradiated by 365 nm light, the colour of FPM
changed from white to yellow, the opposite process occurred
when FPM was heated at 120 oC for ten minutes. This result
assuredly demonstrated that FPM indeed showed photochromic
35 property (Fig. S4).
3.2 IR spectrum of FPM
Fig. 2 (a) IR spectra of pure 2a, FPM (the concentration of 1: 37 wt%, 10 wt%
5 and 4 wt%), and pure 1 range from 3150 cm-1 to 3500 cm-1, and (b) range from
1625 cm-1 to 1725 cm-1 in the solid state, respectively.
The useful IR spectra are employed to confirm that FPM is
composed of 1 and 2a (Fig. 2). As shown in Fig. 2a, broad
absorption bands of 2a in the range of 3000-3500 cm-1 are
10 observed, which suggests that there exist characteristic of schiff
bases with a medium strength intramolecular hydrogen bond in
the solid state.29 Obviously, broad absorption bands of 2a are also
observed in FPM, the result confirms that 2a is one of
components of FPM. The absorption band of 1673 cm-1 can be
15 ascribed to C=O vibration of 1 in Fig. 2b, with increasing
concentration of 1. The intensity of absorption band at 1673 cm-1
increases markedly, which distinctly demonstrates that 1 is one of
components of FPM. So FPM is composed of 1 and 2a. Other
peaks of IR spectra were identified in the experiment section.
Fig. 3 (a) and (b) Absorption spectra and fluorescence emission (λex = 330 nm)
40 changes of FPM (the concentration of 1: 10 wt%) under 365 nm light
irradiation at room temperature in the solid state, respectively.(c) Normalized
emission spectra of 1 (red line), absorption spectra of 2a before 365 nm light
irradiation (blue line) and after 365 nm light irradiation (black line) in the solid
state, respectively.
45 To clearly explain photoswitching mechanism of FPM, the
absorption and fluorescence spectrum of FPM (the concentration
of 1: 10 wt%) have been examined in the solid state. The
absorption and emission spectra of FPM were recorded upon 365
nm light irradiation at room temperature. Fig. 3a, b show that
50 FPM exhibits weak absorption band around 350-470 nm and
strong fluorescence emission at 417 nm before 365 nm light
irradiation, which correspond to the absorption spectrum of 2a
and fluorescence emission peak of 1, respectively. Once 365 nm
light irradiation, FPM can be observed that an absorbing band of
55 2b is increasing around 350-470 nm, which is assigned to the
20 3.3 Photoswitching mechanism of FPM
The helpful FT-IR spectroscopy is used to explain the
photoswitching mechanism of FPM. As shown in Fig. S3A, a
new sharp peak appears at 3400 cm-1 after 2a is irradiated by 365
nm light (curve for b), attributed to the N-H stretching vibration
25 in the pyrazole-ring.18 In addition, a same phenomenon appears in
the FPM, the result indicates that the photoisomerization from 2a
(enol-form) to 2b (keto-form) occurs during 365 nm light
continuous irradiation in the FPM (Fig. S3(B-D)).
The colour of 2a reversibly changed from white to yellow. For
30 FPM, same method was used to evaluate photochromic property
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formation of keto-form isomer of 2a in Fig. 3a. When prolonging
FPM is reversible. So the fluorescence photoswiching efficiency
irradiation time, the emission peak of 417 nm is gradually
diminishing in Fig. 3b. Once the absorption spectra of FPM
increases to the maximum value, which suggests that the energy
transfer rate is basically maximized between 1 and 2b in FPM.
The phenomenon convincingly testifies that the quenching of
fluorescence will occur via energy transfer between pyrazolones
dye and the keto-form isomer of photochromic pyrazolones as
expected. When the fluorescent emission band of pyrazolones dye
of FPM is remarkably improved by controlling reasonable doping
5
10 overlaps well with the absorption spectrum of the keto-form
isomer of photochromic pyrazolones unit (Fig. 3c). Therefore, the
fluorescence emission of 1 is modulated efficiently by the
photoisomerization of 2a with 365 nm light irradiation.30 When
the FPM was heated, the reverse reaction happened from
15 keto-form isomer to enol-form isomer and the absorption band
around 350-470 nm was gradually diminishing, and the
absorption band recovered completely to the original absorption
band intensity, which owes to the excellent fatigue resistance,
thermally reversible properties, and rapid response time of 2a in
20 pure solid state. In agreement with the experiments of naked eye
observation, these results evidently demonstrate that
photochromic pyrazolones works as a modulator for fluorescence
modulation of the pyrazolones dye.
45
Fig. 4 (a) Absorption spectra cycles of FPM (the concentration of 1: 37 wt%,
10 wt% and 4 wt%) during alternating 365 nm light irradiation and colour
fading at 120 oC in the solid state. (b) Fluorescence photoswitching cycles of
FPM (λex = 330 nm) (the concentration of 1: 4 wt% (solid line) and 10 wt%
50 (dash line)) during alternating irradiation of 365 nm light and colour fading at
120 oC in the solid state.
ratio, which also confirms that the 2a regulates the fluorescence
of
1 “on” and “off”. The degradation of fluorescence
3.4 Fatigue resistance of FPM
photoswitching function of FPM was not observed obviously
55 after several months storage. The results indicate that
fluorescence emission of 1 is efficiently modulated by the
photochemical reaction of 2a with high fluorescence quenching
efficiency and remarkable fatigue resistance in the solid state.
The highly optical sensitivity, excellent fatigue resistance and
60 high contrast fluorescence photoswitching properties of FPM are
foundation for designing novel optoelectronic devices.31-34
25 The fatigue resistance of FPM was detailedly studied as follows:
Firstly, the repeatability of the photoreaction of FPM was
assessed. The absorption spectra of FPM (the concentration of 1:
37 wt%, 10 wt% and 4 wt%) were also measured upon 365 nm
light irradiation and heating, respectively (Fig. 4a). When the
30 concentration of 1 is 4 wt% and 10 wt%, the absorption spectra of
FPM is reversible and could go through more than 10 cycles. The
result indicates the photochromic reaction of 2a is not obviously
affected by the presence of 1in FPM. Secondly, if the
fluorescence photoswiching of FPM is also reversible, when
35 veries the amount of pyrazolones dye in photochromic
pyrazolones system. FPM with different doping ratios of 1 was
synthesized and their fluorescence photoswiching property were
measured too (Fig. S5). The fluorescence intensity of
FPM returns completely to the initial value after heating at 120
40 oC, when the concentration of 1 is 4 wt% and 10 wt% (Fig. 4b). It
can be seen noteworthy that the fluorescence photoswiching of
4. Conclusions
In conclusion, we have developed a convenient method for
fluorescence switching of pyrazolones dye, whose fluorescence
65 modulation is realized by energy transfer between fluorescence
dye and keto-form isomer of photochromic pyrazolones under
alternate 365 nm light irradiation and heating at 120 oC. The
fluorescence photoswiching materials can work reversibly
without obviously degradation. The advantages of our system are
70 based on: 1) The pyrazolones dye synthesized shows fluorescence
property and optical waveguide performance, and the
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New Journal of Chemistry
View Article Online
DOI: 10.1039/C5NJ01781E
Photochromic pyrazolones is exploited as a modulator to toggle fluorescence of dye “on” and
“off” based on energy transfer.