A novel photochromic fulgide based on porphyrin for nondestructive information processing

Article abstract of DOI:10.1016/j.cclet.2016.04.025

A fulgide connected to porphyrin (FUL-TPP) can transform its open isomer to closed isomer upon the irradiation with UV or visible light. Herein, they can be used to write binary data. Furthermore, the open form can emit luminescence but the closed cannot form while irradiated in another light that will not cause the optical chemical reaction. Therefore, the data can be read out without destruction.

Full text of DOI:10.1016/j.cclet.2016.04.025

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CCLET 3696 1–4
Chinese Chemical Letters xxx (2016) xxx–xxx
Contents lists available at ScienceDirect
Chinese Chemical Letters
journal homepage: www.elsevier.com/locate/cclet
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Original article
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A novel photochromic fulgide based on porphyrin for nondestructive
information processing
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Q1 Chuan-Ming Yu, Bing-Cheng Hu *, Zhi-Hui Gong, Cheng Liu, Ji-Ting Li
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
A R T I C L E I N F O
A B S T R A C T
Article history:
A fulgide connected to porphyrin (FUL-TPP) can transform its open isomer to closed isomer upon the
irradiation with UV or visible light. Herein, they can be used to write binary data. Furthermore, the open
form can emit luminescence but the closed cannot form while irradiated in another light that will not
cause the optical chemical reaction. Therefore, the data can be read out without destruction.
ß 2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Published by Elsevier B.V. All rights reserved.
Received 7 March 2016
Received in revised form 11 April 2016
Accepted 18 April 2016
Available online xxx
Keywords:
Photochromism
Fulgide
Nondestructive readout
Porphyrin
Chemical transition
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1. Introduction
closed forms to avoid data damage in reading process. Secondly, 30
the readout is based on the emissive luminescence which should 31
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The photochromic molecules have attracted increasing
not cause the photochemical reaction. Obviously, the direct 32
method to resolve the dilemma is to separate the excitation and 33
emission wavelengths from the absorption wavelengths of both 34
isomers. In this article, the porphyrin was used as the luminescent 35
center of fulgide and the method for nondestructive readout will be 36
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attention during the past decades because of their photo-
reversibility [1–3]. Nondestructive readout is one of the most
attractive aims [4] in optical materials for their applications in
optic devices [5]. The fluorescent tuning has been a convenient
mean of modulating the variable properties owing to the fast
response times and high sensitivity [6,7].
Photochromism is defined as reversible chemical transition of a
molecule with irradiation upon appropriate light. Two isomers
show different structures and absorption spectra. Many kinds of
photochromic compounds have been reported in the past decades,
including diarylethenes [8], spiropyrans [9], fulguides [10],
stilbenes [11], azobenzenes [12], etc. Among above, the fulgides
always exhibit favorable thermal stability, high fatigue resistance
and reliable phohochromic reactivity in both solution and even
solid state. The fulgides could be used to store binary information
by ultraviolet and visible light for the application for photo-
information storage due to the excellent photochromic character-
istics. However, two major problems should be resolved for the
application while reading the stored data. Firstly, the exciting light
of readout device would not be absorbed by either the open or the
described in details.
37
Porphyrins [13] are known as natural molecules to exhibit 38
characteristic Soret band in ultraviolet region and Q band in visible 39
region and they will offer luminescence upon excitation. Therefore, 40
they have been recognized as a class of popular luminescent 41
materials that are applicable to bioassays, dyes, photosensitizer and 42
other practical applications. In the case that porphyrin is used as the 43
luminescent center in combination with a fulgide and there will be 44
enough space with no overlap in energy and wave function between 45
the two transitions. Hence, it would be apt to separate the excitation 46
andluminescentfromthetwoisomers. Inthiswork, wewilldescribe 47
how a fulgide based on a porphyrin to constitute a photo-memory 48
molecule with nondestructive readout capability. Porphyrins have 49
been employed as fluorescent reporters in various photochromic 50
molecular frames designed for the similar purposes [14–19].
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2. Experimental
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*
Corresponding author.
To a stirred solution of isopropylidene diethyl succinate (3.0 g, 53
14.0 mmol) in tetrahydrofuran (50 mL) at 0 8C under nitrogen was 54
E-mail address: hubc@njust.edu.cn (B.-C. Hu).
http://dx.doi.org/10.1016/j.cclet.2016.04.025
1
001-8417/ß 2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
Please cite this article in press as: C.-M. Yu, et al., A novel photochromic fulgide based on porphyrin for nondestructive information
processing, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.04.025

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CCLET 3696 1–4
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added NaH (0.8 g, 20.0 mmol) rapidly. The resulting mixture was
stirred for 30 min. The solution of 5-chloro-2-methyl-3-acet-
ylthiophene (1.74 g, 10.0 mmol) in THF (20 mL) was added and
the mixture was allowed to warm to room temperature. After 8 h,
the solvent was removed. The resulting brown syrup was
dissolved in ethyl acetate (50 mL) and acidified with conc. HCl
(10 mL). The reaction mixture was extracted with ethyl acetate
1
.5
(
a)
Write
1.0
(
b)
(2 Â 20 mL). The combined organic layers were dried (MgSO
4
) and
filtered, and solvent was removed in vacuum. The semi-ester
product was dissolved in 10% KOH-alcohol liquor (50 mL) and the
solution refluxed for 2 h. Cold it to room temperature and
acidified with conc. HCl (10 mL). The resulting mixture was
extracted with ethyl acetate (2 Â 20 mL). The combined organic
0.5
Read
Erase
0.0
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400
500
600
700
800
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layers were dried (MgSO ) and filtered, and solvent was removed
in vacuum. The residue was dissolved in anhydrous dichlor-
omethane and acetylchloride (2 mL) was added at ice-cold bath.
After 8 h, the solvent was removed and afforded the target
compound. Purification by chromatography on silica gel with
petroleum ether-EtOAc (1:10) to yield fulgide 1.98 g (66.9%) as
Wavelength (nm)
Fig. 1. UV–Vis absorption spectra of a CH
2
Cl
2
solution of the FUL-TPP: (a) open form,
(
b) closed form.
yellow solid. To a stirred solution of anhydrous CH
2
Cl
2
of fulgide
0.14
(30 mg, 0.1 mmol) and NH -TPP (70 mg, 0.11 mmol), 1 mL of Et N
2
3
0
0
.12
.10
was added dropwise and the mixture was refluxed for 5 h. Cool it
down to room temperature, and 2 mol/L HCl was added to the pH
4ꢀ5. The resulting mixture was extracted with CH
(2 Â 20 mL) and washed with water (3 Â 20 mL) to the pH
7. The combined organic layers were dried (MgSO ) and filtered,
and solvent was removed in vacuum to yield 51 mg (59.2%) as
amaranthine solid. The solid was dissolved in CH Cl (15 mL) and
2 2
Cl
0.08
4
0
0
.06
.04
2
2
2 mL trifluoroacetic anhyride added. The solution turned red to
green rapidly. The mixtures were stirred at room temperature for
another 3 h. After reaction, the solution was removed in vacuum
0.02
.00
0
and the residue was washed with saturated NaHCO
solution, extracted with CH Cl , dried with MgSO and filtered.
The solution was removed in vacuum. Purification by chroma-
tography on silica gel with petroleum ether: CH Cl (5: 1) to yield
48 mg (51.6%) as violet solid. mp: > 250 8C. H NMR (CDCl
500 MHz):
9.04 (s, 2H), 8.78 (s, 6H), 8.41 (s, 2H), 7.92ꢀ7.89 (m,
17H), 7.17 (s, 1H), 2.85 (s, 3H), 2.52 (s, 3H), 2.23 (s, 3H), 1.21 (s,
3
aqueous
0
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Cycles
2
2
Fig. 2. Photocycling of the FUL-TPP in solution of CH
2 2
Cl . The absorbance at
1
,
l = 667 nm measured for 5 s after each switching operation are shown: after UV
irradiation for 2 min (high value) and after visible light irradiation for 20 min (low
value).
3
d
1
3
3
3H), -2.60 (s, 2H); C NMR (CDCl , 127 MHz): d 167.6, 166.6,
166.1, 159.5, 146.8, 142.3, 137.0, 135.6, 134.4, 133.7, 132.0, 131.9,
131.0, 129.1, 128.6, 128.1, 127.9, 125.9, 124.3, 120.1, 119.7, 22.0,
increasing electron density from the gradual formation of the
closed isomer. The green solution was bleached in a large extent
after irradiation with visible light, and a small protuberance arises
at nearly 273 nm. These ring closing and opening cycles were
repeated at least 10 times (Fig. 2). Therefore, the FUL-TPP showed
feasible reversible photochromic reaction (Scheme 2).
The compound FUL-TPP-O can emit fluorescence at 627 nm
when induced with the UV–Vis region (Fig. 3). The excitation
wavelengths exist in a window from 500 to 600 nm. Accordingly,
their closed isomeric forms luminescence quenched while excited
at the corresponding light. Meanwhile, both FUL-TPP-O and FUL-
TPP-C would not be converted to each other under irradiation with
the light in this region. Hence, a nondestructive readout method
would be achieved. Moreover, the emission intensity could be
modulated by actinic reaction between the open and closed
isomers.
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123
21.8, 14.6; IR (KBr)
n: 3455, 3369, 3315, 3052, 3023, 2918, 1812,
1616, 1596, 1510, 1470, 1440, 1349, 1279, 1176, 979, 796, 729,
À1
+
698 cm ; MS(ESI, m/z): 908.24 [M + H] .
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3. Results and discussion
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For the first time, the structure and isomerization of the FUL-
TPP used in this work are shown in Scheme 1. The open form of
FUL-TPP in CH
region. Upon irradiation with UV light (
2
Cl
2
has nearly no absorption band in the visible
= 254 nm), the pink
l
solution turned kelly and a new absorption band appeared around
667 nm ranging from 637 to 714 nm. Another interesting
phenomenon shown in Fig. 1 is that the absorption in Soret band
of porphyrin red shift from 418 to 448 nm of FUL-TPP due to the
Scheme 1. Synthetic route of the FUL-TPP.
Please cite this article in press as: C.-M. Yu, et al., A novel photochromic fulgide based on porphyrin for nondestructive information
processing, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.04.025

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C.-M. Yu et al. / Chinese Chemical Letters xxx (2016) xxx–xxx
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Scheme 2. Photochemical transition of isomeric forms of the FUL-TPP.
procedures as follows. Firstly, we prepared a series of solutions of 138
À7
CH
2
Cl
2
, THF, EtOAc and DMSO of FUL-TPP in about 10 mol/L. 139
They are all nearly colorless but with a little bit red. After 140
irradiation with light at 254 nm for 20 min, they all turned dark red 141
except the solution of CH
the generation of acid by the irradiation upon UV light on CH
order to confirm our prediction, double solutions of CH Cl
2 2
Cl . We predict that the reason may be 142
2
Cl
2
. In 143
2
2
was 144
prepared and one of them was irradiated upon the UV light 145
followed the addition of K CO powder. To the other one, equal 146
2
3
quantity of acetic acid was added carefully and the interface of the 147
two solutions turned green. After vibration, the solutions blend to 148
one phase and show green, then were moved to the UV light. After 149
irradiation for 20 min, the first one with K
2 3
CO turned dark red and 150
the second one with CH COOH turned dark green. To the first one, 151
3
the equal quality of glacial acetic acid was added, after vibration, 152
the solution turned green. The second solution turned red after 153
addition of ammonium hydroxide. The result indicates that the 154
2 2
Fig. 3. Emission spectra of FUL-TPP in solutions of CH Cl (a) the open form and (b)
solution of CH
2 2
Cl of FUL-TPP shows red in acid and green in basic 155
the closed form.
lex = 530 nm, lem = 627 nm.
condition. The irradiation of UV light makes it turned from light to 156
dark and blenched in visible light (Fig. 4).
. Conclusion
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In summary, this work has shown that each of the two isomers 159
of FUL-TPP exhibit the distinctions on structures and spectra. The 160
nondestructive readout method is clearly demonstrated when 161
appropriate light is handled followed by detection of the 162
responding emission after writing binary data for the application 163
in optical information storage and any more photoelectricity- 164
control devices.
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processing, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.04.025