Acid/alkali gated photochromism of diarylethenes with quinoline derivatives

Article abstract of DOI:10.1002/cjoc.201200128

Three new diarylethenes 1-3 combined with quinoline derivatives have been synthesized. Through controlled chemical condition of deprotonation/protonation, they presented some new irreversible photochromic phenomenons under UV/Vis light irradiation in chlo

Full text of DOI:10.1002/cjoc.201200128

COMMUNICATION
DOI: 10.1002/cjoc.201200128
Acid/Alkali Gated Photochromism of Diarylethenes
with Quinoline Derivatives
Song, Boa(宋波)
Li, Haixiaa(李海霞)
Yang, Linb(杨琳)
Zhang, Fushib(张复实)
Xiang, Junhui*,a(向军辉)
a College of Chemistry and Chemical Engineering, Graduate University of Chinese Academy of Sciences, Beijing
100049, China
b The Key Lab of Organic Photoelectrons & Molecular Engineering of Ministry of Education, Department of
Chemistry, Tsinghua University, Beijing 100084, China
Three new diarylethenes 1—3 combined with quinoline derivatives have been synthesized. Through controlled
chemical condition of deprotonation/protonation, they presented some new irreversible photochromic phenomenons
under UV/Vis light irradiation in chloroform solution. It was found that 1—3 had well photoisomerization upon
UV/Vis light irradiation in neutral chloroform solution. Addition of acid to the solution of the ring-opening isomers
of 1—3 produced 1oa—3oa, which performed reversible photochromic behavior under UV/Vis light irradiation and
reversed back to 1—3 under neutralizing with adding lewis base. However, addtion of base to neutral soluton of the
ring-opening isomers of 1—3 produced 1ob—3ob, which could not change to the deprotonated ring-closing
isomers under UV light irradiation.
Keywords diarylethene, photochromism, quinoline, acid, alkali
Introduction
reactivity. Lehn et al.[7] once reported that several di-
arylethenes with phenol and pyridine derivatives, exhib-
ited proton-gated photochromic properities by deproto-
nation and reprotonation of the molecules. The sub-
stituents on heteroaromatics and heteroaromatic forms
influence on the characteristics of diarylethenes. The
diarylethene derivatives have many works reported,
such as pyrrole,[8] thiazole,[9] indole,[10] oxazole,[11] imi-
dazo phenathroline[12] and so on. Quinoline has been
well known for its use in metallic complex materials.[13]
Chen et al.[14] have reported a kind of diarylethene,
which was combined with 3,4-bis(5-formyl-2-methyl-
thien-3-yl)-2,5-dihydrothiophene and 8-hydroxy-2-
methyl-quinoline and had excellent photoisomer under
UV/Vis light irradiation under acid-base effect by the
addition of trifluoroacetic acid or boron trifluoride di-
ethyletherate.
If we can control the isomerization of diarylethene,
the applied range of diarylethene will be more spacious.
In this paper, we have synthesized three novel diary-
lethenes 1—3 (Scheme 1) combined with quinoline de-
rivatives at the 5-position of thiophene ring of diary-
lethene. Deprotonation/protonation could control the
irreversibility of photochromic isomerization of them.
They presented irreversible photochromic properties
under deprotonation condition and reversible behaviors
under protonation/neutral condition.
Photochromic diarylethene[1] has aroused much at-
tention because of the reversible transformation between
two isomers by different wavelength light irradiation. It
could be used in many applications in optoelectronic
devices, such as displays, switches and storages, be-
cause of its advantaged photochromic properties such as
high fatigue resistance, high thermally irreversible
properties, and various physical properties including
absorbance, luminescence refractive index and so on.
Since the photochemical reaction is in generally
proceed in proportion to the number of photons ab-
sorbed by the molecules, the memories or images re-
corded will be destroyed during storage under room
light or after many readout operations. A method that is
strongly desired but still inadequate for circumventing
this problem is gated photochromic reactivity. Generally,
it is hard to keep in an isomer under UV/Vis light irra-
diation. Addition of external stimulations, such as pho-
ton,[2] heat,[3] chemical reaction,[4] electric field,[5] etc.,
to some kind of diarylethenes with special derivative
structures will be able to achieve gated photochromic
reactivity. Addition of acid/alkali is one of the most
usually used chemical methods to control reversibility
of isomerization of diarylethene.[6] So far, some works
have been reported about providing gated photochromic
*
E-mail: xiangjh@gucas.ac.cn; Tel.: 0086-010-88256532; Fax: 0086-010-88256161
Received February 12, 2012; accepted March 19, 2012.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201200128.
Chin. J. Chem. 2012, 30, 1393—1398
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Scheme 1 Synthetic route of three kinds of diarylethene
F2
C
F2C
CF2
OHC
S
S
N
HO
1
F2
C
F2C
CF2
F2
C
N
F2C
CF2
OH
OHC
S
S
heat, Ar, 45 h, (Ac)2O
N
S
S
CHO
OHC
H3COCO
2
F2
C
F2C
CF2
S
S
N
N
HO
OH
3
Table 1 Maximum absorption spectrum (λabs,max, nm), maxi-
mum fluorescence spectrum (λf,max, nm), fluorescence quantum
yield (Φf, %) , optical energy band-gap (Eg,opt, eV) for 1—3 and
DTE in chloroform solution
Results and Discussion
The optical properties of 1 —3 and 1,2-bis(2,5-
methyl-3-thienly)-perfluorocyclopentene (DTE) in
chloroform solution were summarized in Table 1. DTE
has larger Eg,opt and smaller λabs,max because of the
shorter π-conjugated chain. Similarly, 1 and 2 have lar-
ger Eg,opt and smaller λabs,max than 3, too. As known,
DTE, which does not have 8-hydroxyquinoline deriva-
tives, is reversible in acid/neutral/basic solution. None-
theless, the new three diarylethenes have some novel
phenomena, respectively.
The UV/Vis absorption spectrum changes of 1—3 at
room temperature were shown in Figure 1—Figure 6.
The reacting products of the ring-opening isomers of 1
— 3 with trifluoroacetic acid are the protonated
ring-opening isomers of 1—3 (1oa—3oa, Scheme 2).
The mechanism is that N-group of 8-hydroxyquinoline
in 1—3 will react with acid.[4a,7] The reacting products
of the ring-opening isomers of 1 and 3 with sodium hy-
droxide were the deprotonated ring-opening isomers of
1 and 3 (1ob and 3ob, Scheme 2), which could not
transfer to the ring-closing isomers in chloroform solu-
tion. As known, hydroxide radical in 1 and 3 will react
with sodium hydroxide. But the reaction mechanism of
base and 2 is still unclear at present.
a
c
λ
abs,max (ε)
λf,max
Φfb
Eg,opt
3.31
2.14
2.95
1.55
2.99
1.68
DTEod
DTEcd
1o
346 (4.0×104)
502 (2.2×104)
364 (2.9×104)
625 (1.0×104)
365 (3.0×104)
583 (1.3×104)
370 (4.0×104)
650 (1.9×104)
402
0.92
424
423
1.27
1.35
1c
2o
2c
3o
408, 437
0.0761 2.92
3c
1.61
a Exciting wave-length is 365 nm; fluorescence emission spec-
trum of the ring-closing isomers is almost undetectable or very
weak, so the fluorescence quantum yield of the ring-closing iso-
mers is not listed. b Fluorescence quantum yield is detected by a
c
Horiba Jobinyvon Fluorolog spectrometer.
Eg,opt＝1240/λedge
(eV), λedge is the absorption edge wavelength in solution. d Stru-
ctures of DTEo and DTEc were showed in Scheme 2.
visible light, acidification with trifluoroacetic acid chlo-
－
1
roform solution (0.1 mol•L ) and alkalization with so-
－
1
dium hydroxide in methanol (0.1 mol•L ). The proto-
nation and deprotonation effects on 3 were reversible.
3o and 3c, 3oa and 3ca were reversible under UV/Vis
light irradiation. Only 3ob and 3cb were directional
transform: 3cb isomer could change to 3ob upon Vis
The reversibility of 3 with UV/Vis light irradiation in
chemical condition of deprotonation/protonation was
summarized in Scheme 3. 3o, 3c, 3oa, 3ca, 3ob and 3cb
were researched by irradiation with ultraviolet light or
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Chin. J. Chem. 2012, 30, 1393—1398

Acid/Alkali Gated Photochromism of Diarylethenes with Quinoline Derivatives
Scheme 2 Structures of DTEo, DTEc, 1oa—3oa, 1ob and 3ob
F2
C
F2
C
F2C
CF2
F2C
CF2
F2
C
F2
C
F2C
CF2
S
F2C
S
CF2
S
S
S
OHC
S
S
OHC
+
HN
+
HN
S
HO
H3COCO
DTEo
DTEc
1oa
2oa
F2
C
F2
C
F2
C
F2C
CF2
F2C
CF2
F2C
S
CF2
S
S
S
S
+
HN
+
NH
S
OHC
Na+
-O
Na+
O-
Na+
-O
N
N
N
HO
OH
3oa
1ob
3ob
Scheme 3 Schematic diagram of light-operated isomerization of 3 under chemical condition of deprotonation/protonation in chloroform
solution
F2
C
F2
C
F2C
S
CF2
S
F2C
CF2
UV
Vis
S
S
N
N
N
N
-O
O-
O-
-O
3ob
3cb
Deprotonation
Protonation
Deprotonation
Protonation
F2
F2
C
C
F2C
CF2
F2C
S
CF2
UV
Vis
S
S
S
N
N
N
N
HO
OH
OH
HO
3o
3c
Deprotonation
Protonation
Deprotonation
Protonation
F2
C
F2
C
F2C
CF2
F2C
S
CF2
S
UV
Vis
S
S
+
HN
+
NH
+
+
HN
NH
HO
OH
OH
HO
3oa
3ca
Chin. J. Chem. 2012, 30, 1393—1398
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light irradiation; but 3ob could not transform to 3cb
upon UV light irradiation. The mechanisms of the re-
versibility of 1 and 2 with UV/Vis light irradiation in
chemical condition of deprotonation/protonation were
similar, too.
For 1 in Figure 1, the ring-opening isomer of 1 (1o,
the black line, λmax＝364 nm) and the ring-closing iso-
mer of 1 (1c, the green line, λmax＝625 nm) could be
transformed to each other upon UV/Vis light irradiation.
Adding trifluoroacetic acid (in chloroform solution, 0.1
－
1
mol•L ) to 1o would produce a new absorption band
(the orange line, λmax＝420 nm), which was red-shifted
to the absorption band of 1o and deceased in intensity.
Upon irradiation of 1oa with 420 nm light, the propo-
nated ring-closing isomer of 1 (1ca, λmax＝650 nm)
would be obtained whose absorption band also was
red-shifted to the band of 1c. The addition of acid to the
organic photochromic materials, such as spirooxazine,
would change the color of solution and the band of ab-
sorption spectrum in solution, which had been investi-
gated by Fan et al.[15] Oppositely, the addition of sodium
hydroxide (in methanol, 0.1 mol•L ) to the chloroform
neutral solution of 1o produced 1ob, whose absorption
band (the yellow line, λmax＝332 nm), compared to the
absorption spectra of 1o (the black line, λmax＝364 nm)
in chloroform solution was blue-shifted. Upon 365 nm
light irradiation, the 332 nm peak of the yellow line
would reduce in intensity, but there was not any new
band in the 600—700 nm range. It suggested that 1ob
could not transform to the deprotonated ring-closing
isomer of 1 (1cb) under 365 nm light irradiation.
Figure 2 The visible absorption spectrum changes of 1 (2.5×
－
10－ mol•L , CHCl3) with visible light (≥500 nm) irradiation.
5
1
Absorption spectra of 1c (solid), 1cb (dash) and 1ob (dot).
opened form were a little, the main change was de-
creased in the range of 500—700 nm. In the Figure 2,
we could see certain decrease change from 1cb to 1ob in
the range of 500—700 nm. Of course, the main change
was not so obvious as compound 2 and compound 3 in
the Figure 4 and Figure 6. The reason might be the
change speed of compound 1 from 1cb to 1ob. Com-
paring Figure 2 and Figure 4, we could get that addition
of base to compound 1 made the absorption in the range
of 500—700 nm decrease a lot; but for compound 2,
decrease a little. This result implied that 1cb was not
very stable in the solution. Furthermore, addition of base
to compound 1 was operated in the dark condition,
which ruled out the influence of light irradiation. As
known, most kinds of diarylethene were P-type com-
pounds, whose two isomers were thermally stable. But
1cb was T-type compound, which would have certain
decrease in the room temperature and dark condition. As
a result, 1cb decreased in intensity because of the trans-
form from 1cb to 1ob under dark condition, so the ab-
sorption change under visible light irradiation was not
so remarkable, but there existed certain change from 1cb
to 1ob under visible light irradiation. Obviously, the
visible light could make the change from 1cb to 1ob.
Similarly, for 2 in Figure 3, the ring-opening isomer
of 2 (2o, the black line, λmax＝365 nm) and the ring-
closing isomer of 2 (2c, the green line, λmax＝583 nm),
the protonated ring-opening isomer of 2 (2oa, the or-
ange line, λmax＝415 nm) and the protonated ring-clos-
ing isomer of 2 (2ca, the blue line, λmax＝640 nm) could
severally change to each other under UV/Vis light irra-
diation. The absorption spectra of 2oa and 2ca were
red-shifted to those of 2o and 2c, respectively. Rela-
tively, the absorption spectrum of 2ob (the yellow line)
had a maximum absorption peak at 335 nm, which was
blue-shifted compared to that of 2o. Upon exposing to
365 nm light, the 335 nm peak dropped down in inten-
sity and no new absorption band was detected in the 500
—800 nm range. This result indicated that the degrada-
tion of 2ob might take place marginally and 2ob could
－
1
Figure 1 The visible absorption spectrum changes of 1 (2.5×
10－ mol•L－1, CHCl3). Absorption spectra of 1o (black), 1c
5
(green), 1oa (orange), 1ca (blue), 1ob (yellow) and the ring-
opened isomer of 1 with addition of base (red) upon 365 nm light
irradiation.
Addition of base to 1c produced 1cb, whose bands
would decrease in the range of 500—800 nm and almost
did not change in the range of 300—400 nm in intensity
under visible light (＞500 nm) irradiation (Figure 2). It
suggested that 1cb could isomerize to 1ob under visible
light irradiation.
Generally, the absorption changes in the range of
300—400 nm from the ring-closed form to the ring-
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Chin. J. Chem. 2012, 30, 1393—1398

Acid/Alkali Gated Photochromism of Diarylethenes with Quinoline Derivatives
not change to the deprotonated ring-closing isomer of 2
(2cb) under 365 nm light irradiation. Addition of base to
2c produced 2cb, whose bands would decrease in the
range of 300—800 nm in intensity (Figure 4). It sug-
gested that 2cb might simultaneously be degraded and
have partly isomerized to 2ob under light irradiation.
nm light irradiation. 3cb (λmax ＝350 nm, 651 nm),
which was synthesized by 3c addition with base, would
be blue-shifted and decease in the range of 500—800
nm in intensity (Figure 6). It was possibly degraded and
had partly isomerized to 3ob under light irradiation. It
would generate a little flocculent precipitate after visible
light irradiation for a long time, the reason had not been
found out yet.
Figure 3 The visible absorption spectrum changes of 2 (2.7×
10－ mol•L－1, CHCl3). Absorption spectra of 2o (black), 2c
5
(green), 2oa (orange), 2ca (blue), 2ob (yellow) and the
ring-opened isomer of 2 with addition of base (red) upon 365 nm
light irradiation.
Figure 5 The visible absorption spectrum changes of 3 (2.0×
10－ mol•L－1, CHCl3). Absorption spectra of 3o (black), 3c
5
(green), 3oa (orange), 3ca (blue), 3ob (yellow) and the ring-
opened isomer of 3 with addition of base (red) upon 365 nm light
irradiation.
Figure 4 The visible absorption spectrum changes of 2 (2.7×
－
10－ mol•L , CHCl3) with visible light (≥500 nm) irradiation.
5
1
Absorption spectra of 2c (solid), 2cb (dash) and 2ob (dot).
Figure 6 The visible absorption spectrum changes of 3cb (2.0
－
×10－5 mol•L , CHCl3) with visible light (≥500 nm) irradiation.
1
Approximatively, for 3 (Figure 5), the ring-opening
isomer of 3 (3o, the black line, λmax＝370 nm) and the
ring-closing isomer of 3 (3c, the green line, λmax＝650
nm), the protonated ring-opening isomer of 3 (3oa, the
orange line, λmax＝402 nm) and the protonated ring-
closing isomer of 3 (3ca, the blue line, λmax＝720 nm)
were severally reversible upon UV/Vis light irradiation.
But the absorption spectrum of 3ob (the yellow line,
Absorption spectra of 3c (solid), 3cb (dash) and 3ob (dot).
Incorporating perfluorocyclopentene and quinoline
compounds, three diarylethenes that exhibited acid/alkalis
gated photochromic reactivity have been successfully
obtained. It was worthwhile to note that after deprotona-
tion of 1c—3c and then upon visible light (≥500 nm)
irradiation, the resulted 1cb—3cb could convert to 1ob—
3ob, which kept unchanged after UV light irradiation.
However, after addition of acid to the solutions of 1ob—
3ob, they would change to 1o—3o or 1oa—3oa, which
had well reversibility of photochromic reaction.
λ
max＝334 nm) was decreased a little in intensity and no
new increase was detected in the 500—800 nm range
under 365 nm light irradiation, too. It implied that 3ob
might degrade niggardly and could not change to the
deprotonated ring-closing isomer of 3 (3cb) under 365
Chin. J. Chem. 2012, 30, 1393—1398
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COMMUNICATION
Experimental
Conclusions
1H NMR spectra were recorded at 300 MHz with
TMS as an internal reference and CDCl3 as solvent on a
JOEL JNM-ECA300 spectrometer. MS spectra were
recorded in methanol with an ESI-MS Esquire-LC spec-
trometer. UV/Vis absorption spectra were measured
with a Shimadzu UV-2100S UV-Visible recording spec-
trophotometer. An SHG-200 Mejiro precision ultraviolet
irradiate equipment, a PLC-SXE 300 Xenon lamp with
different wavelength filters and an infrared lamp were
used as light sources for photochromic reactions. Fluo-
rescence spectra were recorded by a Hitachi F4500
spectrometer with a setting of 5 nm grating slit and 700
V amplifier of the photomultiplier, and a Horiba Jobi-
nyvon Fluorolog spectrometer with a setting of 1 nm
grating slit at room temperature. 1,2-Bis(2-methyl-3-
thienly-5-formyl)-perfluorocyclopentene was synthe-
sized by our laboratory. Other chemicals for synthesis
were purchased from commercial suppliers. Column
chromatography was performed on silica gel (zcx-2, 200
—300 mesh). All solvents in analytical or chemical
grade were purified from standard procedures.
In summary, we have successfully synthesized three
novel diarylethenes combined with quinoline derivatives
and demonstrated that the quinoline derivatives with
alkyl groups attached to the thiophene heterocycles of
diarylethenes, could undergo a gated photochromic re-
action. The quinoline substituent attached to the
5-position of thiophene heterocycles could react with
acid/alkali and influence on the reversibility of photo-
chromic reaction. Compounds 1—3 could carry out
good photochromic ring-closing reaction with addition
of base.
Ackowlegement
This work was supported by the National Basic Re-
search Program of China (973 Program) with No.
2011CB706900, National Natural Science Foundation of
China with No. 50872149 and No. 50502003, Scientific
Research Foundation for Returned Scholars within the
Ministry of Education of China, and the President
Foundation of the Graduate University of Chinese
Academy of Sciences.
The synthetic methodologies of 1-[2-methyl-3-
thienly-5-(8-hydroxy-2-methylquinoline-2,2'-bithio-
phene)]-2-(2-methyl-3-thienly-5-formyl)-perfluorocyclo-
pentene (1), 1-[2-methyl-3-thienly-5-(8-acetate-2-
methylquinoline-2,2'-bithiophene)]-2-(2-methyl-3-
thienly-5-formyl)-perfluorocyclopentene (2) and 1,2-
bis[2-methyl-3-thienly-5-(8-hydroxy-2-methylquino-
line-2,2'-bithiophene)]-perfluorocyclopentene (3) have
been depicted in Scheme 1. They were prepared ac-
cording to the previously reported method.[14] 1,2-
bis(2-methyl-3-thienly-5-formyl)-perfluorocyclopentene
(450 mg, 1.35 mmol) and 2-methyl-8-hydroxyquinoline
(429 mg, 2.70 mmol) were stirred in acetic anhydride
(30 mL) at 135 ℃ under Ar gas protection for 45 h.
The product was then poured into cold water (50 mL).
The mixed solution was stirred at room temperature for
5 min. The products were extracted with dichloro-
methane (160 mL) and the organic phase was dried with
anhydrous Na2SO4. After evaporation of the solvent, the
targets 1—3 were separated with petroleum/acetone (3/1,
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1
V/V) as extract. Compound 1: H NMR (300 MHz,
CDCl3) δ: 9.86 (s, CHO, 1H), 8.14 (d, J＝9 Hz, 1H), 7.76
(s, 2H), 7.60 (d, J＝8 Hz, 1H), 7.46—7.51 (m, 3H), 7.03
—7.19 (m, 2H), 2.55 (s, 3H), 2.13 (s, 6H). MS (ESI) calcd
for C27H17O2S2NF6 [M ＋ H] ＋ 565.5, found 566.9.
1
Compound 2: H NMR (300 MHz, CDCl3) δ: 9.86 (s,
CHO, 1H), 8.13 (d, J＝8 Hz, 1H), 7.79 (s, 2H), 7.72 (d,
J＝10 Hz, 1H), 7.42—7.55 (m, 3H), 7.02—7.19 (m,
2H), 2.13 (s, 6H). MS (ESI) calcd for C29H19O3S2NF6
[M＋H]＋ 607.5865, found 608.9. Compound 3: H
1
NMR (300 MHz, CDCl3) δ: 8.16 (d, J＝7 Hz, 2H), 7.66
—7.79 (m, 4H), 7.43—7.54 (m, 6H), 6.99—7.19 (m,
4H), 2.01 (s, 6H). MS (ESI) calcd for C37H24O2S2N2F6
[M＋H]＋ 706.7191, found 707.4.
(Cheng, F.)
1398
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© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 1393—1398