Synthesis, mechanism and efficient modulation of a fluorescence dye by photochromic pyrazolone with energy transfer in the crystalline state

Article abstract of DOI:10.1039/c6ra27937f

A dual-responsive photochromic compound, 1,3-diphenyl-4-(3-chloro-4-pyridylformyl)-5-hydroxypyrazole 4-phenylsemicarbazone (1) based on a pyrazolone derivative with excellent reversible photochromic reactions in the crystalline state, was successfully synthesized. The new photochromic mechanism of 1 is attributed to isomerization between the enol form and keto form with proton transfer, which was confirmed by IR, XPS, crystal structure data and theoretical calculation. In order to achieve high-contrast fluorescence switch capability, two-component composite materials (TCCM) were prepared by co-aggregating. The emission intensity of fluorophore 9,10-diphenylanthracene (DPA) can be efficiently switched by the fluorescence resonance energy transfer (FRET) between the donor DPA and acceptor coloured 1 in TCCM. The fluorescence modulation ratio is found to be 79%, which is influenced by changing the content of DPA. This novel photoswitchable TCCM may have potential application as photoswitches.

Full text of DOI:10.1039/c6ra27937f

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PAPER
Synthesis, mechanism and efficient modulation of
a fluorescence dye by photochromic pyrazolone
with energy transfer in the crystalline state†
Cite this: RSC Adv., 2017, 7, 9847
Yinhua Li, Jixi Guo,* Anjie Liu, Dianzeng Jia,* Xueyan Wu and Yi Chen
A dual-responsive photochromic compound, 1,3-diphenyl-4-(3-chloro-4-pyridylformyl)-5-hydroxypyrazole
4-phenylsemicarbazone (1) based on a pyrazolone derivative with excellent reversible photochromic
reactions in the crystalline state, was successfully synthesized. The new photochromic mechanism of 1 is
attributed to isomerization between the enol form and keto form with proton transfer, which was confirmed
by IR, XPS, crystal structure data and theoretical calculation. In order to achieve high-contrast fluorescence
switch capability, two-component composite materials (TCCM) were prepared by co-aggregating. The
emission intensity of fluorophore 9,10-diphenylanthracene (DPA) can be efficiently switched by the
fluorescence resonance energy transfer (FRET) between the donor DPA and acceptor coloured 1 in TCCM.
The fluorescence modulation ratio is found to be 79%, which is influenced by changing the content of DPA.
This novel photoswitchable TCCM may have potential application as photoswitches.
Received 8th December 2016
Accepted 11th January 2017
DOI: 10.1039/c6ra27937f
rsc.li/rsc-advances
development and application of coupling methods are still
restricted by intricate design and synthetic. Therefore, organic
Introduction
19
Due to the high contrast and selectivity of uorescence emission, dyes which are doped into the photochromic system may be
bistable photoswitchable organic molecules such as diarylethene, a good option to attain highly efficacious uorescence switch.
spiropyran, azobenzene and fulgide derivatives are accentuating Intermolecular energy or electron transfer between dyes and
potential applications in uorescence imaging, sensors, optical photochromic moiety can reversibly manipulate the lumines-
1–6
20–23
data storage and molecular switches. The uorescence contrast cence intensity of the uorophore.
of bistable switches is one of the most signicant performance
Most of the composites mentioned above are modulated in
parameters. Therefore, enlargement of uorescence contrast is solution. However, modulation of the uorophore luminescence
crucial to improve resolution and diminish the side effects in solid state is vital for practical application, which can be
destructing the digitalised signals. However, some excellent single sensitively recognized due to its ultrahigh density and selectivity.
molecular photochromic compounds demonstrate weak uores- The pyrazolone derivatives are one of the most promising candi-
cence or low emission contrast and quantum yields under the dates for application because of their photochromic conduct in the
“
common situation”. To this end, many organisations are solid state. However, most of pyrazolones synthesized previously
emphatically engaged in amplifying uorescence contrast showcase irrevocable or partly reversible photochromic reactions
depending on energy or electron transfer from the uorophore to by alternating stimulation of UV light and heating or visible
7–11
24–28
photochromic compound in composites. Further, uorescence light.
In this work, a novel photochromic compound 1 with
contrast can be improved to inhibit destructive reading, which is a substituted pyridine ring on the 4-position of pyrazolone ring was
1
2
one of the primary candidates for multi-addressing sensors,
designed and fabricated. Photochromic compound 1 displays
dual-responded reversible photochromic reactions excluding the
13–15
16–18
ultra-high resolution devices
and non-destructive readout.
In particular, physical doping or coupling strategies are usually poor uorescent contrast in crystalline state. As we know, this is
implemented to manufacture composite materials. However, the rst report on the dual-responded photochromic compound of
pyrazolones. Fluorophore DPA demonstrates high uorescent
emission in crystalline state. More importantly, its emission
spectra superimposed well with the absorption spectra of coloured
Key Laboratory of Energy Materials Chemistry, Ministry of Education, Key Laboratory
of Advanced Functional Materials, Institute of Applied Chemistry, Xinjiang University,
Autonomous Region, Urumqi, Xinjiang, 830046, P. R. China. E-mail: jxguo1012@163. 1. Photochromic pyrazolone 1 might be used to modulate the
com; jdz0991@gmail.com; Fax: +86-991-8588883; Tel: +86-991-8583083
uorescence of DPA. So, TCCM were fabricated by co-aggregating
the uorophore DPA and photochromic compound 1. The uo-
rescence of DPA might be efficiently controlled ON/OFF by the
photochromic reactions of 1 in TCCM based on FRET (Scheme 1).
To the best of our knowledge, FRET is a manifestation of
†
Electronic supplementary information (ESI) available: NMR spectra, kinetics
plot of compound 1; uorescence decay curves, SEM; tables of crystal data,
selected bond length, hydrogen bonds. CCDC 1526956. For ESI and
crystallographic data in CIF or other electronic format see DOI:
1
0.1039/c6ra27937f
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Scheme 1 Schematic diagram of fluorescence modulation for TCCM.
intermolecular energy transfer from the excitation energy of DPA to
coloured 1, which is a non-radiative energy transfer process uti-
29,30
lising physical long-range dipole–dipole coupling.
Experimental section
Materials
4
2
-Phenylsemicarbazide (PSC), 9,10-diphenylanthracene (DPA),
-chloropyridne-4-carbonyl chloride were purchased from
ꢁ
Scheme 2 Synthesis of compound 1, (a) PhNHNH
2
, EtOH, 45 C, 1 h;
(
2
b) 2-chloropyridine-4-carbonyl chloride, 1,4-dioxane, Ca(OH) ,
ꢁ
ꢁ
Aladdin Industrial Corporation. All other materials and solvents 80 C, 2 h, HCl (3 M), r.t.; (c) PSC, EtOH, EtOAc, 80 C, 3 h, r.t.
were purchased from commercial sources and special solvents
were puried with standard procedures.
1
H, pyridine-ring), 7.818 (d, J ¼ 3.6 Hz, 2H, phenyl-ring), 7.548–
7.243 (m, 10H, phenyl-ring).
General
1
,3-Diphenyl-4-(3-chloro-4-pyridylformyl)-5-hydroxypyrazolone
34
Melting point was recorded with a BUCHI M-560 melting point 4-phenylsemicarbazone (1) was prepared with similarly method.
1
13
apparatus. H NMR and C NMR spectra were performed on an The mixture of DP3Cl4PyP (2 mmol) and PSC (2 mmol) were dis-
INOVA-400 NMR spectrometer with DMSO-d as solvent. FT-IR solved in ethanol (8 mL) containing a few drops of glacial acetic
6
ꢁ
spectra were measured by infrared diffuse reectance spec- acid was stirred and reuxed for 3 h at 80 C. Aer cooling down to
troscopy in the range 400–4000 cm on a BRUKER EQUINOX- room temperature, white powders were separated from the solu-
5 spectrometer. The diffraction data were collected at 25 C on tion by ltration, then washed three times with ethanol. Yield:
a Bruker Smart APEX11 single crystal diffractometer equipped 46%. Mp 205.0–206.2 C. H NMR (400 MHz, DMSO-d
ꢀ
1
ꢁ
5
ꢁ
1
): d ¼ 12.018
6
with a 4k CCD-detector (graphite Mo Ka radiation, l ¼ 0.71073 (s, 1H, Pz-OH), 10.188 (s, 1H, N5-H), 9.264 (s, 1H, N4-H), 8.339 (d, J
˚
¼ 5.2 Hz, 2H, pyridine-ring), 7.937 (dd, J ¼ 1.2, 8.8 Hz, 2H, phenyl-
A). Absorption spectra were measured on Hitachi UV-3010
spectrometer. Fluorescence spectra were studied using a Hita- ring), 7.777 (s, 1H, pyridine-ring), 7.600–7.498 (m, 7H, phenyl-ring),
chi F-4500 uorescence spectrophotometer. Fluorescence 7.374–7.251 (m, 6H, phenyl-ring), 7.034 (t, J ¼ 7.6 Hz, 1H, phenyl-
13
decays were recorded on HORIBA FL-3 with 10% attenuation ring). C NMR (120 MHz, DMSO-d
6
): d ¼ 152.124, 150.978,
slices. X-Ray photoelectron spectra (XPS) were carried out using 150.348, 148.762, 147.532, 139.002, 138.577, 137.415, 129.097,
ꢀ
1
a Perkin-Elmer PHI 5300 System. Morphology and microstruc- 128.862, 128.824, 128.596, 126.596, 126.418, 126.000. FT-IR (cm ):
ture of samples were investigated by FESEM (Hitachi S-4800). X- 3364, 3347 n(N–H), 3249 n(O–H), 1653 n(C]O), 1598 n(C]N), 1555,
ray powered diffraction (XRD) patterns were obtained by using 1459 n(phenyl-ring), 1509, 1395 n(pyrazole-ring).
a Bruker D8 advanced instrument equipped with Cu-Ka radia-
tion (l ¼ 0.15406 nm). ZF-8 black-box ultraviolet lamp (6 W) was Preparation of TCCP materials
used as light source with reective lter size is 200 ꢂ 80 mm. A
A stock solution (3 mL) containing pure DPA (0.25 mM) or
compound 1, or mixed solution of compound 1 (2.5 mM) with
different mass ratio DPA (DPA: 0%, 5%, 10%, 15% and 20%) in
ethanol was quickly injected into poor solvent of deionized water
TECH XT-5 melting point apparatus and LED lamp (25 W) were
used as sources for thermal bleaching and visible light-induced
photobleaching, respectively.
(
3
6 mL) under ultrasound. Then, the mixture maintained for 10 h at
Preparation of compounds
ꢁ
0 C to get co-aggregates. The co-aggregates was separated from
ꢁ
35,36
The synthesis processes of the compounds are showed in mixture by centrifugation and dried for 5 h at 50 C in vacuo.
Scheme 2. 1,3-Diphenyl-5-pyrazolone (DPP) was synthesized
31,32
according to the method described in the literature.
,3-Diphenyl-4-(3-chloro-4-pyridylformyl)-5-hydroxypyrazolone
DP3Cl4PyP) was synthesized with analogous method according
Results and discussion
Photochromic properties and mechanism of 1 in crystalline
1
(
33
state
to literature. DP3Cl4PyP was directly used to the next reaction
ꢁ
1
without further purify. Yield: 94%. Mp 82.2–84.1 C. H NMR (400
MHz, DMSO-d
Photochromic properties in crystalline state. The novel
6
): d ¼ 11.354 (s, 1H, Pz-OH), 8.347 (d, J ¼ 4.8 Hz, compound 1 exhibits well dual-response and fatigue resistance
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Fig. 1 Absorbance spectra under UV irradiation (a) and decolouring Scheme 3 Photochromic mechanism of compound 1 ( : neighboring
ꢁ
spectra of compound 1 (b) with visible light or (c) heating at 100 C. (d) molecule).
The colouration-bleaching cycles (red line: UV irradiation; blue line:
heating or visible light).
Structure characterisation and photochromic mechanism
A detailed analysis of photochromic mechanism of compound 1
Scheme 3) was conducted with IR, XPS spectra, crystal structure
data and theoretical calculation as follows. The peak at 3249
performance in crystalline state. The absorption spectra of
compound 1 were examined under UV light irradiation (365
nm) and varying visible light (l > 510 nm) or heating at
a temperature of 100 C. Subsequently, a wide absorption band
appeared and the absorption intensity around 380–500 nm
(
ꢀ
1
cm in IR spectra is assigned to O–H vibration, which shied
to lower wavenumber due to the strong hydrogen bonds within
the crystalline state. Meanwhile, the apparent variation is
ascribed to the isomerization of E-form and K-form (Fig. 3a).
The crest of O–H vibration dissipates under the irradiation due
to the formation of 1b. With an ultimate objective to obtain the
concrete tautomerism of 1, the XPS spectrum was put into
execution to distinguish the isomerization through binding
energy changes of C–O and C]O. Therefore, O 1s spectra
variation of 1 was monitored to verify the photochromic
mechanism (Fig. 3b). The O 1s peak can be sectioned into two
parts by curve tting. The O 1s energy spectrum tting peaks of
ꢁ
continuously increased with the prolonged irradiation time
(Fig. 1a). Meanwhile, the colour transformed from white to
yellow. The colouring process obeys rst-order kinetics with rate
ꢀ
2
ꢀ1
constant 2.26 ꢂ 10
s
for 1 (Fig. S4†). Fig. 1b and c illustrate
that heating or visible light stimulation can decolour the pho-
tostationary state. The variations disclosed that 1 undergoes
photochromic properties because of the photo-isomerisation
from enol form (E-form) 1a to keto form (K-form) 1b in crys-
talline state. The fatigue resistance performance of compound 1
was characterized using UV-vis spectra specifying its high
resistance to light and heat (Fig. 1d). Moreover, the uorescence
properties of compound 1 were further investigated in crystal-
line state. Fig. 2 illustrates the low uorescent contrast of
compound 1.
37
E-form appear at 532.34 and 530.88 eV, which can be assigned
to C–O and C]O, and the integrated areas of energy spectrum
peaks are 71% and 29%, correspondingly. Subsequently, the
binding energies of K-form at 532.72 and 531.28 eV are ascribed
to C–O and C]O, and the integrated areas are 51% and 49%,
Fig. 3 (a) FT-IR spectra of 1 before UV irradiation (black) and after
Fig. 2 Fluorescence spectra of 1 before irradiation (red line) and after (red), (b) XPS spectra of O 1s before (1a) and after (1b) with 365 nm
irradiation (black line) with 365 nm light.
irradiation.
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Fig. 4 (a) The crystal structure and (b) hydrogen-bonded connection
diagram of compound 1.
Fig. 5 The theoretical absorption spectra of K-form I and II with
B3LYP/6-311G(d,p).
respectively. The obvious variation can be implemented to
estimate the photo-isomerization by related integrated areas. molecules were optimised and frequencies were calculated by
The integral areas of C–O increased but integral areas of C]O implementing density functional theory (DFT) following the
decreased for colour-changed compound, reecting the E-form Becke3–Lee–Yang–Parr (B3LYP) with 6-31G(d,p) as basis set. UV-
1a is converted to K-form 1b.
vis absorption along with HOMO and LUMO for six isomers at
Single crystal X-ray diffraction was implemented to analysis optimised geometry in the ground state were executed by
the photochromic mechanism of pyrazolone derivative 1. The employing TD-DFT approach with the B3LYP(54% HF) function
single crystal of 1 was generated using slow evaporation of assorted with the 6-311G(d,p) basis set in the gaseous phase,
ethanol and methanol mixtures (1 : 2 v/v) at ambient tempera- which were listed in Table S4.† The results illustrate that the K-
ture. The crystal data and structure renement details were form I, II and VI demonstrate peak absorptions at the visible
summarised in Table S1.† The corresponding bond length can region. Their absorption spectra are shown in Fig. S9† with
42
be seen (Table S2†). The C7–O1 bond distance is 1.325(4), which Multiwfn analysis. Only the absorption spectrum proles of
is comparable to C–O single bond. The observations further isomers I and II was similar to experimental spectrum. TD-DFT
prove that the sample of colourless 1 exist in E-form. Fig. 4a calculation of I in the gaseous phase predicts three electronic
shows the crystal structure of compound 1, where two solvent transitions at 546, 453 and 403 nm with oscillator strength of
molecules are comprised in the unit of 1. The dimer of 0.0070, 0.0964 and 0.0593 respectively. These absorptions are
compound 1 is formed by alternative intermolecular hydrogen assigned to electron excitations of H / L (99%), Hꢀ1 / L
bond [O(1)–H(1O)/O(2)] as listed in Table S3,† and 1D chains (98%) and Hꢀ2 / L (94%) respectively. Two electronic transi-
are constructed through bridge hydrogen bond of solvent tions of II are 484 and 403 nm with oscillator strength 0.0088
(
Fig. 4b). Further, there exist no inherent hydrogen bonds and 0.2314 for electron excitations of H / L (99%), Hꢀ1 / L
between oxygen and nitrogen through the analysis of the (98%). The maximum values of K-form I and II are at 435 nm
hydrogen bonding in the single crystal structure. Therefore, it is and 397 nm, where, red-shied by ꢃ4 nm and blue-shied by
valid to elaborate the photochromic mechanism of the tauto- ꢃ34 nm for experimental l
values coloured 1 (431 nm)
max
merization process of compound 1 via the multi-proton trans- respectively (Fig. 5). Although the maximum absorption of K-
fers. Firstly, the proton of the O1 atom is transferred to the O2 form I is close to the experiment result, the absorption ranges
atom of the adjacent molecule and the proton of the O2 atom is of II is more nearly experiment spectrum at visible area. This
transferred to the O1 atom of the neighboring molecule via the situation can be attributed to two aspects: (1) the excitation
0
alternative intermolecular hydrogen bonds [O1–H/O2 ]. At the energy is directly dependent on the Hartree–Fock (HF) exchange
same time, the hydrogen of the N4 atom transfers to the N3 percentage.4
3–46
(2) Colour-changed 1 may exist two K-forms of I
atom. And then, the hydrogen of O2 atom transfers to the N4 and II. To this, the calculated relative sum of electronic and
atom through the intramolecular hydrogen bond to form a K- thermal free energies of II with respect to I is analysed. The
ꢀ1
form. In reverse reaction, hydrogen of the N4 atom was trans- relative value is about ꢀ16.30 kcal mol (scale factor ¼ 0.9614),
ferred to O1 atom with the intramolecular hydrogen bond to which indicated that the isomerization reaction from I to II can
form E-form.
be carry out spontaneously. The coloured K-form is conrmed
Quantum chemical calculation is a logical aspect to research according to theoretical calculations, which can further prove
38–40
the correlation between spectra and structure of molecules.
the rationality of our proposed photochromic mechanism.
Hence, we intended to obtain the colour-changed K-form under
some spectroscopic parameters of UV-vis absorption through
relationship spectra-structure to further conrm the rationality
of photochromic mechanism. The six K-form isomers (I, II, III,
IV, V, VI) were constructed on the premise of the E-form single
crystal structure (Fig. S8†). All calculations in this report were
The preparation and switchable properties of TCCM
The preparation and characterisation of TCCM. The TCCM
were prepared with various contents of DPA by co-aggregating
with 67% volume fractions of water le for aging with 10 h.
The preparation details of optimisation condition were recor-
ded in ESI.† Reprecipitates of DPA was also measured following
41
carried out using the Gaussian 09 program. The structure of
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the time (Fig. S10†). Reprecipitates DPA take the shape of the
schistose structure, and the width decrease with prolonging
duration. However SEM spectra of different contents of TCCM
barely possess schistose structure which also indicates that
compound 1 can effectively control the morphology of DPA
(
Fig. 6a). In addition, the typical X-ray diffraction (XRD) of
TCCM with smooth baseline shows signicant differences
Fig. 6b). As the DPA content augments, the diffraction peak at
q ¼ 8.895 degree gradually enhances and is consistent with
patterns of DPA. However, characteristic diffraction peaks for
(
2
Fig. 7 (a) The normalized fluorescence intensities at 445 nm of TCCM
compound 1 have almost no change at all. The results conrm in crystalline state before (black) and after (red) irradiation. (b) Fluo-
that the crystalline of TCCM is basically stable.
rescence spectra changes of doping 10% DPA depending on the
irradiation time, lex: 350 nm.
The uorescence switch properties of TCCM. The uores-
cence spectra were performed to examine the switch properties
of TCCM. Fluorescence intensity of the TCCM was collected at
445 nm before and aer irradiation in crystalline state (Fig. 7a).
The high uorescence contrast can be reected through the
good uorescence modulation rate. The uorescence modula-
4
7,48
tion ratio (FM ratio ¼ 1 ꢀ Ioff/Ion
)
declined with DPA contents
of 5% and 10%, while augmented with a further adding of DPA
content. Besides, when the mole fraction of DPA in TCCM is as
high as 10%, the switch exhibits an excellent uorescence
contrast of 79% in contrast to the crystalline-state 1 (FM ratio ꢃ
6
%). Thus, 10% composites are regarded as an optimised molar
ratio in this study. Fig. 7b shows the uorescence regulation of
0% based on the irradiation time. The results showed that the
Fig. 8 (a) Fluorescence decay profiles of 10% before and after irradi-
ation at room temperature. (b) Fluorescence decay curves of repre-
1
energy donor of DPA could be effectively regulated with FRET cipitates 1 before and after irradiation.
using the photochromic reactions of energy acceptor 1 upon
365 nm light irradiation in crystalline state.
The FRET efficiency can be estimated using the tting
49,50
average lifetime according to eqn (1),
E ¼ 1 ꢀ (s /s )
(1)
T
1 2
here, s and s are deemed as the tting lifetime of TCCM before
1 2
and aer irradiation of 365 nm light irradiation in crystalline
state. The energy transfer efficiency from the excited state of DPA
to the K-form 1b can be weighed using the uorescence life
analysis method. The uorescence decay curves of reprecipitates 1
and TCCM are depicted at 445 nm before and aer the irradiation
at room temperature. The lifetimes of reprecipitates 1 exhibit no
drastic variation before and aer the irradiation, which indicates
that the reprecipitates possess no substantial self-absorbance
Fig. 9 The normalized overlay of emission spectra of DPA (purple line)
and 10% TCCM (blue line) and absorption spectra of 1 before (black
line) and after (red line) under irradiation with 365 nm light.
before and aer irradiation (Fig. 8a). Whereas, the uorescence
decay curves of TCCM evidently exhibit the variations (Fig. 8b and
S11†). The results elucidate that the FRET process takes place in
TCCM. The energy transfer efficiency reaches to the maximum
(55%) for 10% TCCM and the FRET tendency of TCCM is in
contrast with FM ratio (Table S5†). The FM and FRET efficiency
results indicate that the 10% TCCM is a more appropriate ratio.
The impairment of uorescence intensity can be closely associ-
ated with the well superimposed uorescence spectra of uo-
Fig. 6 (a) The SEM spectra of TCCM (A) 5%, (B) 10%, (C) 20%, (D) 30%, rophore with the absorption spectra of K-form 1b (Fig. 9), which
51,52
(
1
b) powder XRD patterns of reprecipitates 1, DPA and TCCM for aging should be benecial for efficient FRET.
0 h.
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1
9 H. Li, J. X. Wang, H. Lin, L. Xu, W. Xu, R. M. Wang, Y. L. Song
and D. B. Zhu, Adv. Mater., 2010, 22, 1237–1241.
Conclusions
The novel dual-responded photochromic pyrazolone compound 20 I. Yildiz, E. Deniz and F. M. Raymo, Chem. Soc. Rev., 2009, 38,
with pyridine ring exhibits great photochromic properties and
1859–1867.
1
fatigue resistance ability in crystalline state. The uorescence 21 Y. Chen and N. Xie, J. Mater. Chem., 2005, 15, 3229–3232.
modulation of TCCM was realised through FRET from energy 22 M. Tomasulo, S. Giordani and F. M. Raymo, Adv. Funct.
donor DPA to energy accepter 1b by photochromic reactions.
The uorescence contrast reaches to 79% with 55% energy 23 E. M. Lee, S. Y. Gwon, Y. A. Son and S. H. Kim, J. Lumin.,
transfer efficiency in optimised molar ratio of 10% TCCM.
2012, 132, 1427–1431.
Based on his high-contrast uorescent switch characteristic and 24 J. X. Guo, L. Liu, G. F. Liu, D. Z. Jia and X. L. Xie, Org. Lett.,
Mater., 2005, 15, 787–794.
inherent feature of photochromic material, TCCM may have
2007, 9, 3989–3992.
potential application for data storage and switch.
25 J. X. Guo, D. Z. Jia, L. Liu, H. Yuan, M. X. Guo, D. L. Wu and
F. Li, J. Mater. Chem., 2011, 21, 12202–12205.
2
6 H. Yuan, J. Guo, D. Jia, M. Guo, L. Liu, D. Wu and F. Li,
Photochem. Photobiol. Sci., 2011, 10, 1562–1567.
Acknowledgements
This work is supported by the National Natural Science Foun- 27 J. X. Guo, Y. C. Zhang, D. Z. Jia, M. X. Guo and Y. H. Li,
dation of China (21571152, 21262038 and U1203292), National
Photochem. Photobiol. Sci., 2016, 15, 1222–1226.
73 Program on Key Basic Research Project of China 28 L. Liu, H. B. Sun, S. Abdurehman, D. Z. Jia, J. X. Guo and
9
(2014CB660805), The Natural Science Foundation of Xinjiang
D. L. Wu, J. Photochem. Photobiol., A, 2013, 267, 55–59.
Uygur Autonomous Region (2013211B04).
29 Q. Liao, H. B. Fu and J. N. Yao, Adv. Mater., 2009, 21, 4153–
4157.
3
3
0 H. Tian and S. J. Yang, Chem. Soc. Rev., 2004, 33, 85–97.
1 B. S. Jensen, Acta Chem. Scand., 1959, 13, 1668–1670.
References
1
G. Berkovic, V. Krongauz and V. Weiss, Chem. Rev., 2000, 100, 32 A. Akbarzadeh and R. Soleymani, Orient. J. Chem., 2012, 28,
741–1754. 153–164.
T. Fukaminato, J. Photochem. Photobiol., C, 2011, 12, 177– 33 J. X. Guo, D. Jia, L. Liu, H. Yuan and F. Li, J. Mater. Chem.,
1
2
208.
2011, 21, 3210–3235.
3
4
H. Li and D. H. Qu, Sci. China: Chem., 2015, 58, 916–921.
C. Yun, J. You, J. Kim, J. Huh and E. Kim, J. Photochem.
Photobiol., C, 2009, 10, 111–129.
Y. Yokoyama, Chem. Rev., 2000, 100, 1717–1740.
M. Irie, Chem. Rev., 2000, 100, 1685–1716.
34 H. Liu, J. X. Guo, D. Z. Jia, M. X. Guo, L. Liu and D. L. Wu,
New J. Chem., 2015, 39, 9866–9871.
35 Q. Liao, H. B. Fu, C. Wang and J. N. Yao, Angew. Chem., Int.
Ed., 2011, 50, 4942–4946.
36 H. Tong, Y. Dong, M. H ¨a ußler, J. W. Y. Lam, H. H. Y. Sung,
I. D. Williams, J. Sun and B. Z. Tang, Chem. Commun., 2006,
10, 1133–1135.
5
6
7
8
B. H. Rau, Angew. Chem., Int. Ed. Engl., 1973, 12, 224–235.
M. Han and M. Hara, J. Am. Chem. Soc., 2005, 127, 10951–
1
0955.
F. M. Raymo and M. Tomasulo, Chem. Soc. Rev., 2005, 34,
27–336.
37 E. Ito, H. Oji, T. Araki, K. Oichi, H. Ishii, Y. Ouchi, T. Ohta,
N. Kosugi, Y. Maruyama, Y. Naito, T. Inable and K. Seki, J.
Am. Chem. Soc., 1997, 119, 6336–6344.
9
3
1
1
1
1
1
0 G. Y. Jiang, S. Wang, W. F. Yuan, L. Jiang, Y. L. Song, H. Tian 38 S. A. Bhat and S. Ahmad, J. Mol. Struct., 2016, 1105, 169–177.
and D. B. Zhu, Chem. Mater., 2006, 18, 235–237.
1 S. J. Lim, J. Seo and S. Y. Park, J. Am. Chem. Soc., 2006, 128,
39 M. Karabacak, M. Cinar, M. Kurt, A. Poiyamozhi and
N. Sundaraganesan, Spectrochim. Acta, Part A, 2014, 117,
234–244.
14542–14547.
2 S. Z. Pu, H. C. Ding, G. Liu, C. H. Zheng and H. Y. Xu, J. Phys. 40 M. Karabacak, Z. Cinar, M. Kurt, S. Sudha and
Chem. C, 2014, 118, 7010–7017.
3 A. J. Myles and N. R. Branda, Adv. Funct. Mater., 2002, 12,
N. Sundaraganesan, Spectrochim. Acta, Part A, 2012, 85,
179–189.
1
67–173.
41 M. J. Frisch, G. W. Trucks, H. B. Schlegel, et al., Gaussian 09
revision A.01, Gaussian Inc, Wallingford, CT, 2010.
4 J. Karnbratt, M. Hammarson, S. Li, H. L. Anderson,
B. Albinsson and J. Andreasson, Angew. Chem., Int. Ed., 42 T. Lu and F. Chen, J. Comput. Chem., 2012, 33, 580–592.
2
010, 49, 1854–1857.
43 M. Walker, A. J. A. Harvey, A. Sen and C. E. H. Dessent, J.
Phys. Chem. A, 2013, 117, 12590–12600.
44 E. Vessally, S. S. Amiri, A. Hosseinian, L. Edjlali and
A. Bekhradnia, Phys. E, 2016, 87, 308–311.
1
1
1
1
5 M. Berberich, A. M. Krause, M. Orlandi, F. Scandola and
F. Wurthner, Angew. Chem., Int. Ed., 2008, 47, 6616–6619.
6 E. Deniz, S. Sortino and F. M. Raymo, J. Phys. Chem. Lett.,
2
010, 1, 1690–1693.
45 A. J. Cohen, P. Mori-S ´a nchez and W. Yang, Chem. Rev., 2012,
112, 289–320.
46 J. Beheshtian, Z. Bagheri, M. Kamroozi and A. Ahmadi,
Microelectron. J., 2011, 42, 1400–1403.
7 A. Reisch, P. Didier, L. Richert, S. Oncul, Y. Arntz, Y. M ´e ly
and A. S. Klymchenko, Nat. Commun., 2014, 5, 4089.
8 K. Trofymchuk, L. Prodi, A. Reisch, Y. M ´e ly, K. Altenh ¨o ner,
J. Mattay and A. S. Klymchenko, J. Phys. Chem. Lett., 2015, 47 M. Bossi, V. Belov, S. Polyakova and S. W. Hell, Angew. Chem.,
, 2259–2264. Int. Ed., 2006, 45, 7462–7465.
6
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4
8 J. Folling, S. Polyakova, V. Belov, A. van Blaaderen, 51 B. K. An, S. K. Kwon, S. D. Jung and S. Y. Park, J. Am. Chem.
M. L. Bossi and S. W. Hell, Small, 2008, 4, 134–142. Soc., 2002, 124, 14410–14415.
9 M. Tramier, I. Gautier, T. Piolot, S. Ravalet, K. Kemnitz, 52 F. G. Shen, A. D. Peng, Y. Chen, Y. Dong, Z. W. Jiang,
4
J. Coppey, C. Durieux, V. Mignotte and M. C. Moisan,
Biophys. J., 2002, 83, 3570–3577.
Y. B. Wang, H. B. Fu and J. N. Yao, J. Phys. Chem. A, 2008,
112, 2206–2210.
50 A. Hoppe, K. Christensen and J. A. Swanson, Biophys. J.,
2002, 83, 3652–3664.
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