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Photochromic Materials: More Than Meets The Eye
Junji Zhang, Qi Zou, and He Tian*

levels have recently attracted many atten-

Photochromic materials are a family of compounds which can undergo
reversible photo-switches between two different states or isomers with
remarkably different properties. Inspired by their smart photo-switchable
characteristics, a variety of light-driven functional materials have been
exploited, such as ultrahigh-density optical data storage, molecular switches,
logic gates, molecular wires, optic/electronic devices, sensors, bio-imaging
and so on. This review commences with a brief description of exciting
progress in this field, from systems in solution to modified functional sur-
faces. Further development of these photo-switchable systems into practical
applications as well as existing challenges are also discussed and put in
prospect.
1. Introduction
Photochromism is the term used for a reversible photo-induced
transformation of a molecule between two isomers whose
absorption spectra are distinguishably different.[1] During the
reversible photoisomerization, some physical properties of pho-
tochromic compounds, such as absorption spectra, fluorescence
emission, conjugation, electron conductivity, electrochemical
properties, magnetic properties, coordination properties, dipole
interaction, refractive index, dielectric constant and geomet-
rical structure may be tuned by light.[1,2] This has enlightened
people to apply this kind of compounds to perform as photo-
chemical molecular switches. Usually, molecular switches act
as switching units in various optoelectronic devices and func-
tional materials are addressed by stimulating it with light, elec-
tricity or chemical reagents to specifically switch the physical
properties between two states.[3] So far, photochromic materials
are very fascinating in fields such as molecular logic gates,[4]
data recording and storage,[5] multi-photon devices,[6] surface/
nanoparticle devices,[7] photo-electronic devices,[8] electro-
chemical wiring,[9] etc. Thus, further creation of optoelectronic
and photo-optical devices based on photochromic molecular
switches which operate at both molecular and supramolecular
J. Zhang, Q. Zou
Key Laboratory for Advanced Materials
and Institute of Fine Chemicals
East China University of Science & Technology
Shanghai 200237, P. R. China
Prof. H. Tian
Key Laboratory for Advanced Materials
and Institute of Fine Chemicals
East China University of Science & Technology
Shanghai 200237, P. R. China
E-mail: tianhe@ecust.edu.cn
DOI: 10.1002/adma.201201521
tions. Apart from these, photo-switchable
compounds also have played an important
role in sensing,[10] self-assembly[11] and
photo-controlled biological systems.[12]
Some of the most promising classes of
photochromic materials are shown in
Figure 1. Among diverse photochromic
compounds, dithienylethene derivatives
have been intensively investigated for sev-
eral decades from the fundamental and
practical points of view for their numerous
potential applications as opto-electrical
devices owing to their excellent fatigue
resistance and thermally irreversible prop-
erties, high cyclization and cycloreversion
quantum yields, rapid response as well as reactivity in the solid
state.[13] The properties and applications of these photochromic
materials have been recently reviewed.[1,2a,3,13,14]
In this review, we will highlight noticeable achievements
over the past decade in the field of photochromic materials,
especially dithienylethene derivatives for the design of advanced
materials. This article will not include all accomplishments in
this research field but rather points to important developments
by selecting a few representative examples from different
research areas.
2. Photochromic Molecular Switches
2.1. Photochromic Switches as Multi-Addressable Materials
The goal of miniaturizing functional materials down to mole-
cular level is currently a very hot research field, since it could
result in a remarkably improved performance as a consequence
(a)
UV
Vis
R R S S
S S R R
(b)
UV NO2
N O NO2 Vis N
R R
O
(c)
N N
N UV
N Vis
Figure 1. Photochromism of Dithienylethene (a), Spiropyran (b) and
Azobenzene (c).

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O
N Junji Zhang was born in
O 1985 and completed his BSc
studies in Applied Chemistry
(2007) at East China
University of Science and
S S Technology, China. He is cur-
1 rently working on the last year
for his PhD degree under the
Figure 2. Molecular structure of compound 1. supervision of Prof. He Tian.
His research interests are
of ultrahigh density of functional molecules compared to that mainly focused on the devel-
of current devices.[3] Among all the molecular devices, multi- opment of photochromic
addressable materials for computing systems, such as logic materials and molecular switches.
gates,[15] data storage systems[16] and field-effect transistors,[17]
aroused a wide spread interest in scientific research. Light as
an energy-efficient, environment-friendly and ultrafast power Qi Zou received a Msc degree
source, would provide a bright future for the application of in Chemistry from Nanjing
photo-induced materials. As a result, a large number of multi- University of Science and
addressable photochromic switches have been reported.[4,5] Technology, Nanjing, China,
Tian’s group reported a photochromic multiple addressing in 2006. He is currently pur-
memory in a single molecular system of dithienylethene with suing his PhD degree under
two pyridinium moieties.[18] By taking advantage of the fact that the supervision of Prof. He
zinc(II) ion and protons can induce obviously different absorp- Tian in East China University
tion and fluorescence spectra of the photochromic molecule of Science and Technology,
under sequential alternate UV/Vis light irradiation, a compli- Shanghai, China. His research
cated molecular switch with four optical outputs responding interests lie in the field of
to four inputs is realized by a single compound. Although this photochromic materials and
system was still working in solution and some of the inputs fluorescent sensing materials.
are ions, which could bring in salt waste after several cycles of
operations, this pioneer work provides a brand-new view for the Prof. He Tian received his Ph.
future to design and construct “wet” computers that mimic cer- D. degree in 1989 from East
ebral behaviors. China University of Science &
The thermal stable dithienylethene derivatives with a six- Technology, China. From 1991
membered aryl-ring bridge[19] also exhibit excellent photo- to 1993, he stayed in Siegen
chromic properties and logic operation potential. Zhu et University as a postdoc
al constructed a joint NOR-INHIBIT logic gate based on a supported by Alexander
dithienylethene derivative containing naphthalimide as the von Humboldt Foundation.
center ethene bridge 1 (Figure 2).[20] Due to the solvatochromic In 1999, he was appointed
property of naphthalimide bridging group, 1 emits fluorescence Cheung Kong Distinguished
in different wavelengths as the polarity of the solvent changes. Professor by the Education
In this logic operational system, UV light (λ = 365 nm) and Ministry of China. His current
solvent polarity (acetone/hexane in%) were applied as Input1 research interests include the syntheses of novel functional
and Input2, respectively. The fluorescence at λ = 420 nm and organic dyes and development of interdisciplinary mate-
λ = 530 nm, which were modulated by alternate UV/Vis irradia- rials science that determines the electronic and optical
tion and variation of solvent polarity, were labeled as Output 1 properties of materials. Prof. Tian is currently Co-Editor of
and Output 2, respectively. Thus, a photochromic and solvato- Dyes & Pigments and International Advisory Board Member
chromic NOR-INHIBIT joint logic gate was constructed. for Polymer Chemistry and Chemical Science. In 2011,
Zhu and Chen recently synthesized a novel photo- he was selected as a member of the Chinese Academy of
chromic terarylene 2 (Figure 3) containing a fluorescent Science.

benzo[b]thiophene-1,1-dioxide bridging unit, which allowed

access to multiple states triggered by metal ions (mercury(II),
copper(II)), protons and light.[21] A series of multi-addressed
molecular materials, such as half-adder, half-subtractor,
Figure 3. Molecular structure of compound 2. encoder/decoder and multiplexer/demultiplexer, have been

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Figure 4. All-photonic molecular encoder-decoder 3.
constructed on this unimolecular platform. Yet, the major
challenge for this versatile unimolecular multi-addressed
system is how to apply it to practical devices in the solid
state.
In fact, more complicated system such as molecular keypad
lock and encoder-decoder can be constructed based on multi-
photochromore systems.[21–23] Moore, Gust and coworkers
reported a dithienylethene triad which covalently linked to two
fulgimide units 3 that performed as an all-photonic single bit
4-to-2 encoder and 2-to-4 decoder.[23a] As for the encoder, four
light stimuli of different wavelength (460 < λ < 590 nm, λ =
302, 366, 397 nm), which can maneuver the alternate isomeri-
zation of dithienylethene and fulgimide moieties, were defined
as Input 0 to Input 3, respectively. And two specific absorption
peaks at wavelength of 475 and 625 nm were labeled as Output
0 and Output 1, respectively. When performed as the decoder,
two different wavelengths of light stimuli (λ = 302, 397 nm)
were selected as Input 0 and Input 1, respectively. As for the
four outputs of the decoder, two specific absorption wave-
lengths (λ = 393, 535 nm), transmittance at one wavelength (λ =
535 nm) and fluorescence emission at 624 nm were applied
(Figure 4). Recently, a more complicated multifunctional and
reconfigurable system (eg. AND, XOR, INH, half-adder, half-
subtractor, multiplexer, demultiplexer, encoder, decoder, keypad
lock and logically reversible transfer gate logic devices) based
on the same molecule with a common initial state has been
reported.[23b] It should be highlighted that, this multifunctional
Figure 5. Isomerization of dithienylethene-diporphyrin complex 4.
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logic operation system is all-photonic. Switching between dif-
ferent binary states is achieved with irradiation of different
wavelengths and output signals are either absorbance or fluo-
rescence at certain wavelengths. This eliminates the access of
additional materials (such as acid, base, salt etc.) to the gate
element and therefore implements the integration of multiple
logic systems and circuits in a single molecule and permits
in principle monolithic three-dimensional arrays of molecular
devices.
One of the most pressing problems addressed in the molec-
ular data storage is how to store the information without con-
comitant loss of data, which is referred to as non-destructive
readout.[24] To achieve this goal, Andréasson and coworkers
constitute a dithienylethene-zinc porphyrin dimer 4 supramo-
lecular system with a potential application in future non-
destructive data storage devices.[25] As shown in Figure 5,
after alternative UV/Vis irradiation, each of the two 4 isomers
formed a structurally distinct complex with the porphyrin
dimer. Since the major spectral shift of this complex occurred
in a region beyond the photochromically active absorption
bands of dithienylethene, the isomerization-induced absorp-
tion and emission changes, which were used as output signals,
were easily probed without affecting the state of any isomers.
Hence, this supramolecular system optically controlled the
“write-read-erase” operation with a non-destructive readout
process.
Non-destructive readout can also be realized by two-photon
modulation. Song, Tian and coworkers described a novel spiro-
naphthoxazine 5 with a much more stable open-ring photo-
merocyanine form by incorporating a ferrocene moiety in the
parent spironaphthoxazine (Figure 6).[26] A high storage density
3D recording utilizing two-photon technology with 5 was real-
ized. This is the first example of realization of practical informa-
tion storage utilizing spirooxazine derivatives. Considering the
inherent reversible photoisomerization and high fatigue resist-
ance of 5, a promising candidate for future storage of optical
information with the capability of repeated “re-recording” was
provided in this work.
Belfield and coworkers demonstrated a dithienylethene
and fluorene 6 derivative doped poly[methylmethacrylate-co-
(diethylvinylbenzylphosphonate)] (PMMA-co-VBP) multiple
layer system implemented in non-destructive multiple rea-
dout of 3D data storage (Figure 7).[27] The photo-reversible
readout of this photochromic polymeric storage medium can
be done for greater than 104 cycles without
significantly compromising the stored data,
on account of the application of two-photon
modulated fluorescence as readout signal.
Besides the non-destructive readout ability,
another prominent advantage of two-photon
storage system is that data can be recorded
and read out using the same wavelength,
compared to those in which read and write
wavelengths are well separated. Therefore,
the different operations between recording
and readout are simply realized by changing
the intensity of irradiation, which makes the
design of future molecular memory device
more convenient and applicable.
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Figure 6. Photoisomerization of spironaphthoxazine derivative 5.
Figure 7. Structures of two-photon absorption fluorene derivative 6.
2.2. Photochromic Switches with Ion Recognition Ability
The surge of interest has been aroused by photochromic
switches based on dithienylethenes combined with the concept
of molecular recognition in supramolecular chemistry. Coordi-
nation of dithienylethene ligands opens up new perspectives
for the design of photo-switchable molecules.[28]
Based on our previous work,[18] some new photochromic
switches with ions recognition ability were developed. Our
group[29] reported a dithienylethene derivative 7 (as depicted in
Figure 8) composed of N-butyl-1,8-naphthalimide and pipera-
zine, which exhibited multi-responses to UV irradiation, proton
and copper(II) ions. Taking advantage of the intramolecular
fluorescence resonance energy transfer (FRET) and photo-
induced electron transfer (PET) processes, compound 7 could
mimic a soft gear-shift operation based on alternative UV/Vis
irradiation, protonation/deprotonation and copper(II) ion com-
plexation/dissociation. The complexation of compound 7 with
copper(II) ion transformed dithienylethene moieties into the
photo-inactive parallel form and this operation could mimic the
parking (P) state.
As an active area in supramolecular chemistry, the devel-
opment of sensors with photochromic properties, which may
overcome the problem of one-time use probes, has received
increasing attention because of their wide applications in the
fields of environment science, photoelectric materials and
biological medicine. Several photochromic compounds as ver-
satile sensors for ions have been reviewed by Giordani and
Natali.[30] Due to limitations on space, herein, we just focus on
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representative dithienylethene derivatives functionalizing as
sensors, which are not described in the related review.[30] Our
group reported two chemosensors 8 and 9 based on structur-
ally unsymmetrical dithienylcyclopentene,[31] which responded
to UV/Vis light, mercury(II) and fluoride ions (Figure 9). Com-
pounds showed excellent optical properties and distinguished
mercury(II) and fluoride ions with high selectivity and sensi-
tivity. It was found that their photochromic properties could be
modulated by mercury(II) and fluoride ions. Moreover, com-
pounds in photostationary states became promising sensors
for mercury(II) and fluoride ions with high selectivity. Unfor-
tunately, addition of ions could not induce a large spectral shift
in open-ring and closed-ring forms, which is one of the most
desired properties for light-controlled chemosensors.
As a basic binary unit, the molecular switch combined with
molecular sensing offers a possibility for establishing elec-
tronic logic devices. Recently, our group designed a structurally
unsymmetrical dithienylethene 10,[32] which was considered as
a fluorescent “turn-on” chemosensor to detect copper(II) and
cyanide ions based on complexations (Figure 10). Addition of
copper(II) ion to the solution of 10 could result in the fluores-
cence enhancement. Sequential addition of cyanide anion to
the solution of 10-Cu2+ induced a further increase in the fluo-
rescence intensity. Additionally, its photochromic properties
were tailored by copper(II) and cyanide ions, respectively. Based
on UV irradiation, copper(II) and cyanide ions coordination as
inputs and fluorescence signals as outputs, a complicated logic
circuit was proposed to carry out complex logic operation and
a molecular keypad lock depending on the input sequence was
successfully constructed to protect information at molecular
scale. This work provides deeper insights for the future design
of unsymmetrical photochromic dithienylethene derivatives as
multifunctional nanoscale logic devices.
Switching of host-guest interactions by means of photo-
irradiation potentially enables detection of certain chemical
species, for instance, metal ions. Chen and Liu[33] reported
a dithienylethene derivative 11 with an imidazole unit as the
ligand for metal ions (Figure 11), which could be used as a
bifunctional chemosensor to independently detect copper ion
by quenched fluorescence recognition in open-ring form and
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Figure 8. The photoswitching processes of compounds 7 with proton, copper(II) ions and light stimuli.
sodium or potassium ion by colorimetric recognition in closed-
ring form. The composition of the chemosensor could be
manipulated by photo-modulation, which resulted in changes
in the upper detection limits. Unfortunately, there was no
explanation for the interaction mechanism between sodium
or potassium ion and compound 11 in closed-ring form. This
Figure 9. Multi-responses mechanism of compounds 8 and 9 to
mercury(II), fluoride ions and light stimuli.
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work provides a useful design strategy for the tuning of sensing
properties by light irradiation.
Recently, the coordination of photochromic derivatives with
ions to modulate the photochromic reactivity has drawn much
attention. Huang and Li, et al.[34] reported an organoboron-
based dithienylethene derivative 12 which photochromic
property could be modulated by the addition of fluoride and
mercury(II) ions. As shown in Figure 12, the highly selective
binding ability of compound 12 with fluoride and mercury(II)
ions allowed the modulation of its spectral properties, both in
its open-ring and closed-ring forms. The special Lewis acid-base
interaction between a trivalent boron atom and a fluoride anion
caused obvious absorption spectral changes of 12 in both open-
ring and closed-ring forms. The modulation mechanism by
mercury(II) ion was attributed to the complexation interaction
between mercury(II) ion and sulfur atom. Compound 12 was
derived from a structurally symmetrical analogue consisting of
two organoboron moieties attached to the dithienylethene unit
and the studies on its selective interaction with fluoride anion
were reported by the same authors.[35] In a sense, compound 12
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and its analogue may be considered as potential chemosensors

Figure 10. The sensing processes of compound 10 with copper(II) and
cyanide ions and the corresponding changes in the fluorescence.
for ions sensing.
There is a stunning example of anions binding ability tuned
by switching between the open and closed isomers of a function-
alized dithienylethene derivative. Yin and Liu, et al.[36] reported
a versatile amide- and urea-functionalized dithienylethene
derivative 13 which exhibited excellent photochromic properties
(Figure 13). As anion receptors, compound 13 could recognize
halide anions, and display switchable affinities for chloride and
bromide anions upon alternate irradiation of ultraviolet and vis-
ible light. The higher affinity of the open-ring isomer for chlo-
ride and bromide anions was ascribed to a smaller cavity for the
complexation of chloride and bromine anions with the amide-
and urea-ligands. This enlightening work supplies a novel
model for the design of supramolecular hosts with switchable
recognition function.
The host-guest interaction is usually accompanied by the flu-
orescence signal which allows its reversible detection and fully
controlled by photoirradiation. Pu and coworkers[37] synthe-
sized two structurally unsymmetrical perfluorodithienylethene
derivatives 14 and 15 bearing a Rhodamine moiety (Figure 14).
Through the intramolecular fluorescence resonance energy
transfer (FRET) process, compounds showed multi-state
responses to UV/Vis light and proton. Their fluorescence
emission intensities could be modulated by proton and UV/
Vis stimuli. Moreover, compounds were applied to construct
the molecular logic circuit with three inputs (UV/Vis light and

Figure 11. Bi-functional metal chemosensor 11. Figure 13. Compound 13 and its switchchable affinities for halide
anions.

Figure 12. Photochromic processes of compound 12 modulated by F− and Hg2+.

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Figure 15. Molecular structures and the photochromic process of the
co-assembly 16.
Figure 14. The fluorescence switching principle of compounds 14 and 15
with Cr(III), Al(III), Ca(II) ions and proton.

proton) and one fluorescence output. Additionally, the signifi- Subsequently, Huang and Yi, et al.[41] reported a co-assembly
cant color and fluorescence changes of compound 14 could be of the naphthalimide based gelator 17 and dithienylethene
selectively triggered by Cr(III), Al(III) and Ca(II) ions, due to attached melamine 18 by virtue of the triple parallel hydrogen
the ring-opening of the Rhodamine moiety. bonds (Figure 16). The self-assembly structure of 17 varied with
different kinds of solvents. Addition of 18 to the self-assembly
of 17 induced the change of the morphology of the complex
2.3. Self-assembly Based on Photochromic Materials from flaky texture to films, which sequentially transformed to
aggregated flakes upon the irradiation of 365 nm light. The flu-
As an important field of supramolecular chemistry, sponta- orescence of the co-assembly could be tuned by alternative irra-
neous self-assembly of small molecules into complex super- diation of UV/Vis light. Moreover, the wettability of the surface
structures by various noncovalent interactions has attracted prepared by the co-assembly could be switched by light stimuli.
much interest as it is a powerful approach towards the develop- This work provides further insights to fluorescence and mor-
ment of new materials and devices. Photo-controlled methods phology controlling, which makes it promising for application
are an attractive alternative since they provide a very broad in smart responsive materials.
range of tunable parameters, such as wavelength, duration and
intensity.[38]
Huang and Yi et al.[39] reported a fluorescent switchable self-
assembled system 16 based on dithienylethene derivative by
the formation of hydrogen bond between pyridine groups and
carboxylic acid moieties (Figure 15). Fluorescence enhance-
ment was observed in all of these assembled systems including
in solution, in solid state as well as in nanoparticles. The solid
state fluorescence of the assembly was effectively switched by
alternative irradiation with UV and visible light. Furthermore,
the “concentration quenching” problem in the solid state was
alleviated due to the hydrogen bond formation and an energy
transfer process, accompanied by a 65 nm blue shift of the fluo-
rescence. If the problem of the slow response to UV light in
solid film could be solved, this self-assembled system would
preferably realize the nondestructive readout operation by the
control of the fluorescence intensity in a reversible manner. In
addition, our group also designed an analogue supramolecular
photoswitch with UV/Vis light as inputs and electrochemical
signals as outputs, built from dithienylethene derivative 16 and
carboxyl attached tetrathiafluvalene (TTF-COOH) via intermo-
lecular hydrogen bond.[40] Figure 16. Molecular structures of the co-assembly.

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Figure 17. Proposed ring-opening cyclic monomer of compound 19.
Some researchers have devoted an effort to supramolecular
polymers based on dithienylethenes, since such polymer pos-
sess unprecedented distinct new material properties owing to
their dynamic reversible characteristics. Wang and co-workers[42]
reported a dithienylethene derivative 19 containing quadruple
hydrogen-bonding ureidopyrimidinone (UPy) unit, which
afforded linear assemblies in solution and underwent concen-
tration-dependent ring-opening polymerization (Figure 17). The
two UPy groups of compound 19 could form a cyclic monomer
with two thienyl rings fixed in a parallel conformation, which
prohibited its photo-cyclization. Moreover, a mixed polymer
film as a fluorescent switch with non-destructive readout ability
for data storage and high-resolution imaging technology was
fabricated by mixing compound 19 with a naphthalimide based
fluorescent dye to form the linear photochromic assemblies
through quadruple hydrogen bonds.
2.4. Photochromic Dithienylethenes with Aggregation-Induced
Processes
Recently, one encouraging achievement is made by using a spe-
cial class of fluorophores showing a gradually enhanced fluo-
rescence emission with increasing concentration, a so-called
“aggregation-induced enhanced emission” (abbr. AIEE), which
may solve the problem of “concentration quenching” in the flu-
orescence signal.[43]
Park and co-workers[44] first reported unconventional fluo-
rescent dithienylethene molecule 20 exhibiting the property
of aggregation-induced enhanced emission (Figure 18). A
dithienylethene derivative containing 1-cyano-trans-1,2-bis(4’-
methylbiphenyl)ethylene was synthesized and its fluorescence
performance was examined in the aggregated state as well as in
solution. In solution, the derivative was nonfluorescent, while it
showed a strongly enhanced fluorescence in the aggregated state
as well as bistable photochromism. Moreover, the contrast (>10)
on/off fluorescence switching was successfully implemented in
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the size-tuned neat nanoparticles of 20 and
also in a PMMA film highly loaded with 20.
Subsequently, Park and coworkers[45] reported
a series of π-conjugated cyanostilbene deriva-
tives based on dithienylethenes, suggesting
a unique self-assembly motif for molecular
nanostructures with AIEE. Such aggrega-
tion or self-organization effects have received
increased attention as all-around building
blocks for a variety of self-assembled organic
nano-optoelectronics devices.
Fukaminato and Irie[46] reported a pho-
tochromic dithienylethene derivative 21
linked to perylene bisimides fluorophore
which could modulate fluorescence changes
upon photochromism induced aggregation
(Figure 19). It was found that the aggregate
formation was influenced by photo-irradia-
tion. The aggregates were dissolved owing to
irradiation with UV light and the aggregate
formation was dependent on the configura-
tion of the dithienylethene unit. By molecular
calculations, they considered that an increase in the electronic
densities of the maleimide moiety in the closed-ring isomer of
21 suppressed aggregate formation and that the geometrical
change of the dithienylethene unit affected the aggregate for-
mation to some extent. Consequently, the characteristic aggre-
gation was observed to be a function of the concentration and
the temperature, and aggregate formation was affected by the
photochromic reaction.
2.5. Dithienylethenes with Gated Photochromic Properties
Irie and coworkers[47] reported a dithienylethene derivative
with two propionyloxy groups undergoing photo-isomerization
in ethanol, in which a rigid intramolecular hydrogen bonding
formed in cyclohexane fastened the molecule into the parallel
Figure 18. Molecular structure of compound 20.
Figure 19. Molecular structure of compound 21.
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Figure 20. Molecular structures of compounds 22 and 23.
conformation and made it photochemically inactive. This is
the first report on dithienylethenes with gated photochromic
reactivity, which is a strongly desirable property for the applica-
tions in optoelectronic devices, high-density optical memories,
addressable polymers, and smart materials. The gated reactivity
is the property that the On/Off photo-activity of molecules is
dependent on the external stimuli, such as heat, reaction or
coordination.
Two dithienylethene derivatives (compounds 22 and 23
depicted in Figure 20) with temperature gating of the ring-
opening process were developed by Dulić and Feringa et al.[48]
By exploring the temperature dependence of the photochemical
behavior of compounds 22 and 23, it was firstly found that
photochemical ring-opening process was strongly temperature
dependent and below ca. 130 K, the photochemistry was effec-
tively suppressed, whereas the ring-closing process showed little
temperature dependence. They revealed a key parameter associ-
ated with the reversibility of these molecular systems by virtue
of UV-Vis kinetics experiments over the temperature range
115-290 K for photochromic switches. Such strong temperature
dependence of the ring opening implies that variation of tem-
perature might be applied to the gating of the photochromic
behavior of dithienylethenes.
Light is an effective trigger for the release of active chem-
ical and biological species from masked, innocuous forms[49].
Branda and coworkers[49a] developed a new approach to light-
triggered delivery of chemical species based on integrating
reactivity-gated photochemistry with photo-gated reactivity.
As shown in Figure 21, in reactivity-gated photoswitching,
dithienylfulvenes 24a and 24b were not photoswitchable, and
Figure 21. Representation of the selective and sequential photo-release system.
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they could spontaneously undergo thermal Diels-Alder cyclo-
additions with alkene 25 to result in the formation of racemic
26a and 26b that could convert to their thermally stable closed-
ring forms 27a and 27b, respectively. Thus, the thermal reaction
gated the photochemistry. In photo-gated reactivity, the reverse
Diels-Alder reactions only proceeded from the open-ring forms
of compounds 26a and 26b, because 27a and 27b lacked the
cyclohexene structures required for the fragmentation reac-
tions. Thus, the photochemistry has gated the thermal reaction.
Additionally, because 27a and 27b absorbed different types of
visible light, selective and sequential release may be achieved
by modulating the light source to trigger the ring-opening reac-
tion of only one of the ring-closed compounds.
As one of the reaction approaches, using esterification/
hydrolysis to control the photochromic reactivity has been
reported by Irie and coworkers.[50] Dithienylethene deriva-
tives 28 and 29 did not exhibit any photochromic behavior in
cyclohexane upon irradiation with 405 nm light, indicating that
the photochromic reactivity was strongly suppressed by the
intramolecular proton transfer from the phenol hydrogen to the
carbonyl oxygen (Figure 22). Addition of acetic anhydride could
trigger the photochromic reactivity because the protection of a
hydroxyl group with an ester group interrupted the intramo-
lecular proton transfer. Such chemically gated systems may
be applied to display materials, memory media and molecular
logic devices.
In addition, Branda and coworkers[51] reported an analogue
(compound 30 depicted in Figure 23) whose photochromism
was suppressed by the formation of the intramolecular hydrogen
bonding between the phenol hydrogen and the carbonyl oxygen
in cyclohexane. 30 worked equally well in solution and in an
immobilized state when exposed to vapors of an organophos-
phate to generate colorless compound 31, which underwent
ring-closing when exposed to UV light and produced an easily
observable change in color. So this “chemically-gated” photo-
responsive compound 30 could be used as a colorimetric sensor
for the naked-eye detection of organophosphorus nerve agents.
The basic principle for regulating photo-activity of
dithienylethenes is based on the reversible processes of lim-
ited/unlimited rotation of the two pensile heterocyclic rings.
Li and coworkers[52] reported a chemically gated system based
on regulation of the intramolecular interactions. As shown in
Figure 24, selective oxidization of the sulfur atoms in the mole-
cule 32 induced the formation of strong intramolecular hydrogen
bonding interactions and the steric hindrance resulting from
S,S-dioxide moieties. These two factors stabilized and enriched
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Figure 22. The photochemical behavior of compounds 28 and 29.
Figure 23. The photochemical behavior of compounds 30 and 31.
the photo-inactive parallel conformation in solution, resulting
in completely suppressed photochromic reactivity of 33. This
process could be considered as a “lock” process. In an “unlock”
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Figure 24. The photochemical behavior of compounds 32 and 33.
process, reactivated photochromic reactivity was obtained by
deoxidization of the S,S-dioxide moieties in the molecule 33,
which unfastened the two pensile thiophene rings in the photo-
inactive conformation. Accordingly, the photochromic activity
of such chemically gated dithienylethene switch system could
be manipulated by a reversible process between the oxidation
state and the reduction state.
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Figure 25. The photochemical behavior of compound 34.
REVIEW
The gated photochromic reactivity controlled by coordina-
tion/complexation is preferred for the application in the opto-
electronic field relative to heat and reaction, because the coordi-
nated gated system possesses some virtues, such as the simple
operation strategy, the economical complexing agent, as well as
the reversible gated photochromic reactivity tuned by compl-
exation/dissociation. Recently, Zhu and coworkers[53] reported
a dithienylethene derivative 34 whose photochromic reactivity
gated by complexation with BF3 (Figure 25). Compound 34
exhibited a typical photoisomerization upon the alternate
irradiation with UV and visible light. Addition of BF3•Et2O
to the solution of 34 could promote the rotation of the thia-
zole rings in molecule 34 to coordinate with BF3, resulting in
a rigid seven-membered ring. A longer distance between the
two active carbon atoms simultaneously made the geometry
closer to the photo-inactive parallel conformer. Consequently,
the photochromism was prohibited and the “lock” gate was
achieved by the formation of the photochromically deactivated
rigid boron-coordination conformation. Furthermore, adding
Et3N to the complexation solution could play a role as a “key”
to the “lock”, which selectively interrupted the coordination of
34 with BF3 and recovered the original char-
acteristic photochromism.

2.6. Photochromic Switches for Potential

Biological Application

As described in previous sections, photo-

chromic materials have a wide application
in sensing, logic operation, supramolecular
construction etc. based on the modulation of
fluorescence and other properties. In order to
make photochromic materials more practical,
implementation of photochromic functional
derivatives into biological fields, such as cell
imaging,[54–56] enzyme activity and paralysis
modulation,[57,58] has attracted many atten-
tions recently.
The sensitivity of in vivo fluorescence
imaging, generally limited by autofluores-
cence, absorbance, light scattering and penetra-
tion depth, has been improved significantly by
employing switchable probes.[59] Irie and Soh
synthesized a photo-switchable protein label
based on dithienylethene derivative with a
fluorescein fluorophore and succinimidyl ester
unit 35.[60] The fluorescence of the labeled pro-
tein can be reversibly switched by alternate UV/
Vis light (Figure 26). Since the fluorophore can
be easily converted to other functional groups,
such as an Ni2+-preloaded bis(nitrilotriacetic
acid) (NTA-Ni2+) unit which is a specific recog-
nition unit for histidine, this precedent work
provides a perspective for future functional
labeling and imaging of biological system with
photo-switchable materials.
Figure 26. (a) Chemical structure of 35. (b) Photo-switching of fluorescence in 35 labeled Yi and Zou developed a new amphiphilic
biomolecule 36 based on the photochromic reaction. dithienylethene 37 with hydrophilic and

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Figure 27. Structure and photochromic process of 37.
Figure 28. Molecular structure of compound 38.
hydrophobic chains at two ends and applied it as a photo-switch-
able probe for imaging living KB cells (human nasopharyngeal
epidermal carcinoma cell) with the confocal laser scanning micro-
scopy (CLSM), using Rhodamine B as a reference (Figure 27).[54a]
The amphiphilic dithienylethene 37 forms stable vesicle nanos-
tructures in aqueous solution and can enter the living cells with
low cytotoxicity, which is essential in clinical applications. This
Figure 29. The molecular structure of 39 and Cy3.
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photochromic vesicle exhibited switchable fluorescence between
open and closed states in KB cells, indicating a potential utility as
a cellular marker or fluorescence switch in living cells with high-
ratio signal change and excellent resistance to fatigue.
Tian, Yi and coworkers demonstrated new visible-light-
modulated phosphorescence bioimaging probes based on pho-
tochromic iridium complexes containing a dithienylethene
unit 38.[54b] Dithienylethene iridium complex with switchable
luminescence was reported recently.[61] In order to optimize the
water-solubility of dithienylethene iridium complex, 2-picolinic
acid was used as the ligand (Figure 28). The distinctive wave-
length of excitation as well as long luminescent lifetimes of
iridium phosphorescence switchable complexes as cell imaging
probes provide an opportunity to overcome limitations including
short-wavelength excitation and autofluorescence. The exist-
ence of metal-to-ligand charge-transfer transitions (3MLCT)
may extend the excitation wavelength for photoisomerization
of dithienylethene to the visible area, thus affording more bio-
friendly conditions. Besides the cell-permeation and photo-
bleaching, the cytotoxicity which is another critical character-
istic for bio-systems was also studied. It was found that, more
than 90% of the imaged cells remained their cellular viabilities,
indicating a low cytotoxicity of this phosphorescent complex.
Kim and coworkers reported that dithienylethene 39 cross-
linked polyamidoamine (PAMAM) dendritic nanoclusters, mod-
ified with Cy3 as a label dye, were used for in vivo fluorescence
imaging in living zebra fish and cells with a high on-off con-
trast (Figure 29).[55] In this work, two routes, permeation and
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Figure 30. Structure of Cu-complex 40.
microinjection, were used to internalize the biocompatible fluo-
rescent nanostructure effectively into a biological system, which
was highlighted as the first example of this kind. Another advan-
tage of this work is that the treatment and injection of theses
photo-switchable nanoclusters into living cells and organisms
are very simple compared to those requiring complex biological
manipulations. Furthermore, the non-toxicity and unnoticeable
immunogenic concerns also meet the requirement for clinical
application. Except for the advantages mentioned above, this
work provides exciting potential applications based on this nan-
ocluster system as well. First, multiple simultaneous sensing
could be accomplished by attachment of various targeting groups
to the surface of these nanoclusters. Second, proper structural
modification of photochromic cross-linker could realize the
tuning of photo-switching at a desired wavelength.
Apart from in vitro cell imaging, other biological properties
such as enzyme activity[57] and paralysis[58] can also be modu-
lated by photochromic materials. Branda and König presented
a dithienylethene derivative decorating with sulfonamide and
copper(II) iminodiacetate 40 as a photochromic mimic for
carbonic anhydrase I(hCAI), as shown in Figure 30.[57] The
sulfonamide group in 40 acted as the inhibitor, and the role
of copper(II) iminodiacetate component was to reversibly coor-
dinate to the imidazole side chains of the histidine residues
exposed on the protein surface close to the Zn(II) active site
of the enzyme and help dock the sulfonamide inhibitor group
into the catalytic center. Due to the flexibility of ring-open form
40o, it is allowed to simultaneously dock the sulfonamide and
the copper(II) iminodiacetate components onto the enzyme
active site. However, for the ring-closed counterpart 40c, the
resulting rigid backbone forced the two components away from
each other in a nonproductive manner, allowing only one of the
components to bind to the enzyme at a time, therefore reduced
inhibition behavior. It is noteworthy that in this work the open
isomer is the inhibitor, and the visible light is applied to acti-
vate the inhibitor. This should be highlighted since visible light
performs better penetration into tissue and reduces the amount
of damage caused by higher energy UV light.
Figure 32. The photochemical behavior of compounds 42a-42e.
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Figure 31. Structure of compound 41.
Branda and coworkers incubated C. elegans, a living organism,
with pyridinium tethered dithienylethene 41 and studied the
in vivo photo-switchable paralysis induced by alternate UV/
Vis irradiation (Figure 31).[58]C. elegans appeared paralyzed and
immobile when 41 was in its closed form, while after photo-
decyclization to the open isomer less paralysis was observed.
Thus, the photo-controlled on-off of biological functions was
achieved. According to the electrochemistry experiment, the
closed-ring isomer appears to be the better electron acceptor.
Therefore, the different electron-accepting ability between the
two isomers may be the mechanism of inducing the interrup-
tion of the metabolic electronic pathway. This example illus-
trates how photoswitches offer great potential for advanced bio-
medical technologies such as photodynamic therapy as alterna-
tive, noninvasive surgical treatments.
2.7. Liquid Crystals and Photonic Crystals Based on
Photochromic Dithienylethenes
The tuning of the structure and optical properties of liquid-crys-
talline (LC) media by virtue of light have aroused wide research
interest recently in the development of electro-optic devices.
Liquid-crystalline with photochromic behavior in molecular
systems affords a promising approach to applying in optical
technological devices. So far various types of photo-responsive
liquid crystals have been reported.[62] However, it is still a great
challenge to design such photo-responsive liquid crystals being
useful in molecular devices and optical data storage systems.
Space constraints permit only representative works which have
not been described by Ref [62a] to be cited.
Photochemically switch the chirality in liquid crystals is
intriguing for the dynamic control of the electronic and optical
properties in nanoscale materials. Recently, Akagi and cow-
orkers[63] reported the photo-responsive chiral dithienylethene
derivatives (compounds 42a-42e as depicted in Figure 32)
bearing two axially chiral binaphthyl moieties and used them
as chiral dopants to induce the chiral nematic liquid crystals
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Figure 33. The fluorescence switching principle of compound 43 with light stimuli.
(N∗-LCs). The conformational change of the dithienylethene
moieties in the local space around the 2-position of the binaph-
thyl moieties via photoisomerization after alternative irradia-
tions with UV and visible light resulted in a reversible change
in the dihedral angles of the binaphthyl rings. In accompany
with the photochemical isomerization, the N∗-LCs including
(R)-42a and (S)-42a exhibited a reversible helical inversion in
the screw sense. The N∗-LCs including (R)-42b and (R)-42c
displayed a reversible photo-switching in the phase transitions
between N∗-LC and N-LC. The N∗-LCs including (R)-42d and
(R)-42e showed an obvious change in the helical pitch accom-
panied by photo-isomerization. Notably, (R)-42a and (S)-42a are
the first chiral dopants to induce a helical inversion in an N∗-LC
by the photo-isomerization of the dithienylethene moiety.
Considerable attention has been paid to develop introducing
photonic crystals (PCs) due to their special light manipula-
tion properties. Modulating spontaneous emission by using
the photonic top-band of a PC is of particular interest. By
studying the optical properties of dithienylethene derivative
43 and coumarin-loaded PMMA film on the PC surface, Song
et al.[64] demonstrated a facile approach to amplifying fluores-
cent contrast by introducing PCs into optical memory. This film
adopted 43 as a photochromic switch and the coumarin as an
available fluorescent dye. As depicted in Figure 33, when these
two components are mixed in a film, the coumarin acted as
an energy donor and the closed-ring form of 43 was an energy
acceptor. On/off switching of the fluorescence resulted from
an intermolecular energy transfer from the fluorophore to the
photochromic unit under optical stimulation. Thus, a 40-fold
enhancement of fluorescence signal and a 7-fold on/off ratio
amplification relative to the glass were realized due to the effi-
cient extraction and large surface areas of the PC. Moreover, the
fluorescence image of recording marked on the PC exhibited
both high brightness and contrast, indicating that the PC sur-
face did amplify fluorescent contrast effectively to attain high
resolution and sensitivity.
3. Photochromic Switches on Surfaces
3.1. Surface Functionalization with Photochromic Materials
A major goal of molecular electronics is to make use of single
molecules that function as switches on metal surfaces. This
requires the development of molecules which can reversibly
switch between two conductive states in response to an external
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Figure 34. Attachment of dithienylethene to the gold surface.
trigger. Light is a very attractive external stimulus for such
switches due to its easy addressability, fast response times and
compatibility with a wide range of condensed phases.[65] Pho-
tochromic materials, which undergo reversible isomerization
under different wavelength of lights, qualify to be a potential
candidate in surface molecular electronics. So far, a great ideal
of works have been done with photochromic materials as sur-
face conductor switches.
Feringa and co-workers linked dithienylethene molecule
onto the gold surface {Au (111)} and successfully controlled
the reversible conductance switching with alternate UV/Vis
light (Figure 34).[66] The different photochromic behaviors of
dithienylethenes directed linked to gold surface via different
aromatic spacers have been further investigated.[67] The effi-
ciency of photochromic reactions are influenced and slowed
down after anchored to the gold surface due to the quenching
of the excited state. The dithienylethenes with benzene spacers
at both meta-/para- sites performed a bi-directional photo-
reaction, yet thiophene bridged dithienylethene performed a
uni-directional photo-reaction. This demonstrated that small
changes in the molecular structure could have an enormous
impact on the overall photochemistry.
Willner, Tian and coworkers constructed an electro-active
and photo-isomerizable dithienylethene monolayer associated
with a Au electrode which acted as a Write-Read-Erase infor-
mation processing system and as a flip-flop Set/Reset memory
element (Figure 35).[68] In this dithienylethene associated elec-
trode system, the open form 44o could act as an information
recording interface. The information was encoded electrochem-
ically by either electrochemically-induced or photochemically-
induced isomerization to closed form 44c. The encoded infor-
mation could be read out by Cyclic Voltammetry (CV) spectra
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REVIEW
Figure 35. Assembly of 44 on the electrode surface, electrochemical ring-
closing into 44c and photochemical ring-opening into 44o.

and the stored information was erased by a photochemical step

that transformed 44c to 44o. The analysis of the electrochem-
ical/photochemical properties of the monolayer-functionalized
electrode revealed a unique system, where electronic or optical
signals may lead to Write-Read-Erase functions. Figure 36. Dithienylethene derivative 45 based electrochemical/photo-
Willner and Yehezkeli reconstituted apo-glucose oxidase on a electrochemical switchable wired glucose oxidase electrode and the struc-
photo-isomerizable dithienylethene-FAD (Flavin adenine dinu- ture of amino-FAD.
cleotide) monolayer linked to a gold electrode leads to the phot-
onic wiring of the enzyme with the electrode and to the optical/
electrochemical switching of the bio-electro-catalytic functions Another molecular wire device between nanoscale electrodes
of the enzyme (Figure 36).[69] As the catalytic active site FAD based on a dithienylethene photo-switch 47 and α-cyclodextrin
is surrounded with insulating protein structures of glucose (α-CD) polyrotaxane 48 was developed through interconnec-
oxidase (GOx), an electron mediator is need for the transfer tion by Kawai and Taniguchi.[71] The photo-triggered reversible
of electrons from the active site to the electrode. In this work, conductivity changes of the molecular wire 49 originated from
dithienylethene derivative 45 was used as a photo-switchable the photoisomerization of dithienylethene switch center. The
mediator. The open isomer of 45o performed as a better elec- interconnect method (Figure 38), which combines several func-
tron mediator while the closed isomer 45c, generated either tional molecules, allows the production of molecular wires with
by electrochemical or photochemical cyclization, had a much various device properties that can be well modulated.
lower electrochemical activity. Therefore, a molecular wire that
switched between a charge-transporting state and an insulating
configuration by means of external photonic or electrical sig-
nals were designed.
A chemical functionalization of hydrogen terminated silicon
(111) surface with photochromic dithienylethene using an eth-
ylene moiety as the anchoring group was achieved by Nishihara
and co-workers (Figure 37).[70] This system underwent photo-
chemically reversible current changes upon alternate irradia-
tion with UV/Vis light. Conductive atomic force microscopy
was used to measure the current changes on the modified
silicon electrodes. The closed isomer 46c showed a relatively
higher current value than that of the open isomer, which indi-
cated a better conductance of closed isomer compared to the
open counterpart 46o. The reversibility of current switching
upon irradiation was directly related to the π-conjugation
change between the open and closed dithienylethene isomers.
Understanding the interplay between the molecular structures
and the switching properties can provide firm design principles Figure 37. Current changes of the 46o and 46c surfaces by UV and vis-
for the creation of optoelectronic devices. ible light.

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Figure 38. Self-organized interconnect method for molecular wires 49.
Recently, photo-controlled uptake and release system[72] has
attracted more and more attentions due to their potential appli-
cation in treatment of pollutants. An optic/electrochemical
molecular imprinting gold nanoparticles (Au-NPs) matrix based
on dithienylethene derivative 50 was reported by Willner and
Zhang as a molecular “sponge” (Figure 39).[73] On accounts of
the lengthened conjugation structure of the closed isomer 50c,
it exhibits the property of an electron acceptor. This facilitates
the interaction between the closed isomer and Au-NPs matrix
which contain bis-aniline donor groups as linking bridges
via π-donor/acceptor interactions. The open isomer 50o, on
the other hand, lacks electron acceptor feature, thus is desta-
bilized and released from the donor-bridged Au-NPs matrix.
This leads to the photo-controlled release of substrate from the
polymer matrix. For the electrochemically controlled process,
dithienylethene substrates stay in its closed acceptor isomer
form, while the initial donor bridges are varied between their
oxidized acceptor (quinone) and reduced donor forms (bis-
aniline). The π-donor/acceptor interaction between the Au-NPs
matrix and substrates are disturbed reversibly, giving the elec-
trochemically switched uptake and release of imprinted mol-
ecules, or molecular “sponge” behavior.
Spiropyran, as another branch of photochromic materials,
also plays an active role in photo-switchable functionalized sur-
face materials.[74] Martínez-Máñez and co-workers modified the
mesoporous MCM-41 framework with photochromic spiropyran
derivatives 51 for the photo-controlled release of substrates.[75]
Spiropyran 51-sp undergoes a reversible photo-isomerization to
its zwitterionic merocyanine 51-mr isomer under the irradiation
of UV light (Figure 40). In this system, Ru(bipy)32+ was used as
the substrate stuffed in the mesoporous MCM-41 framework
and the negatively charged generation 1.5 poly(amidoamine)
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(G1.5 PAMAM) dendrimers were designed as nanoscopic
molecular stoppers. When the anchored spiropyran derivatives
were in their zwitterionic merocyanine form, they interacted
with negative-charged G1.5 PAMAM dendrimers via an elec-
trostatic interaction and blocked the Ru(bipy)32+ from releasing
from the mesoporous MCM-41 framework. Irradiation of the
system with the visible light turned the merocyanine isomers
back to neutral spiropyran form, resulting in the dissociation of
the blocking dendrimers from the MCM-41 and a consequent
release of Ru(bipy)32+ to the outside solution. Visible absorption
spectrum was used as the monitor of the release process.
3.2. Photo-functional Nanoparticles modified by
Photo-switchable Materials
In nanotechnology, nanoparticles (NPs) are defined as particles
sized between 1-100 nm and behave as a whole unit in terms
of their transport and properties. Nanoparticles are of great
scientific interest as they are effectively a bridge between bulk
materials and molecular-sized materials. Nanoparticles possess
unexpected optical properties such as size-dependent absorp-
tion/emission in quantum dots (QDs), quantum confinement
in semiconductor particles, surface plasmon resonance in some
metal particles (eg. Au-NPs) and superparamagnetism in mag-
netic nanoparticles (MNPs), etc. Recently, nanoparticles directed
photo-switches, bio-sensors, catalytic modulations, molecular
imprinting, data storages and solar cells have attracted many
attentions in various scientific areas.[72b,74b–74d,76] In this chapter,
we reviewed several representative works on the optic modula-
tion of nanoparticle properties by photo-switchable species tog-
gled nanoparticles.
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Figure 41. The “remote control” process using the UV light generated
under high excitation power densities and the visible light generated
under low excitation power densities when UCNPs absorb near-infrared
light (980 nm).

Branda and coworkers employed lanthanide-doped core-

Figure 39. Photochemical (a) and electrochemical (b) uptake and release
of 50 into and from the imprinted Au-NPs matrix.
Figure 40. Structure and photochromic reaction of spiropyran derivative
51.
shell-shell upconverting nanoparticles (UCNPs) to reversibly
toggle a pair of dithienylethene photoresponsive molecules in
a “remote-control” fashion using a single wavelength of near-
infrared light (λ = 980 nm) and by adjusting only the excita-
tion power (Figure 41).[77] The key aspect was the nonlinearity
of the upconversion mechanisms, which results in the selective
generation of UV and visible light under high-power and lower
power densities, respectively. The high-power infrared irradia-
tion of UCNPs generated UV light at λ = 365 nm, which trig-
gered the ring-closing reactions of dithienylethenes. Conversely,
the ring-opening reactions of dithienylethenes were triggered
simply by reducing the power density of the excitation infrared
light to the UCNPs, when visible light was generated. Through
the combination of core-shell-shell UCNPs and dithienylethene
photochromics, the photo-switchable system that could be mod-
ulated simply with the power of the excitation light was created.
This discovery offers a highly convenient and versatile method
to spatially and temporally regulate photochemical reactions
using a single light source and changing either its power or its
focal point.
A biocompatible and stable photoswitchable quantum
dots (QDs) was developed by Jares-Erijman and coworkers.[78]
Dithienylethene derivative was utilized as the photo-modulator
after covalently linked to an amphiphilic polymer which self-
assembles with the lipophilic chains surrounding commer-
cial hydrophobic core-shell CdSe/ZnS QDs (Figure 42). Since
the amphiphilic polymer capping had a hydrophobic region
between the QD surface and a hydrophilic exterior of the pol-
ymer coat, this enabled the phase transfer of this QD from an
organic to an aqueous medium without notable decrease in all
desirable properties of the original QD. This particular structure
allowed the introduction of hydrophobic functional molecules,
such as dithienylethene, into the QDs system. Furthermore, the
luminescence intensity could be modulated by dithienylethene
units attached in the amphiphilic polymer coating by Förster
Resonance Energy Transfer (FRET) after cyclic irradiation of
UV/Vis light. The modulation of emission was about 35-40%,
which could be further optimized by achieving greater overlap

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Figure 42. Photoswitching QDs coated with an amphiphilic photo-
chromic polymer, which fluorescence is modulated by the FRET with UV
and visible light irradiations.
between QD emission and dithienylethene absorption as well
as by additional dithienylethene tailoring allowing for better
conversion rates and closer placement to the QD surface.
Wang and Jiang presented a spiropyran-AuNP 52 based
resettable and multi-readout logic system that includes AND,
OR and INHIBIT logic operations (Figure 43).[79] As mentioned
before, spiropyran can undergo reversible photoisomerization
between neutral spiropyran 52-sp and zwitterionic merocyanine
52-mr isomers under alternate irradiations of UV/Vis light. The
merocyanine isomer has been reported to have a coordination
ability with several metal ions such as copper (II) and ferric
(III) ions.[80] Therefore, the complexation of metal ions between
merocyanine photoisomer ligands triggered the aggregation of
Au-NPs. In this logic system, UV/Cu2+ (AND), Fe3+/Cu2+ (OR)
and Cu2+/EDTA (INHIBIT) were used as Input signals, respec-
tively. On the other hand, the ratio between the absorption at
λ = 520 nm and λ = 670 nm, which is characteristic for the
aggregation form, was defined as the Output signal. The dis-
tinctive advantage of this system is that molecular events in
aqueous solution could be translated into a color change of the
solution, which can be monitored by several readouts, such as
UV/Vis spectroscopy, zeta potential, dynamic light scattering
(DLS) and even with the naked eye.
Besides inorganic nanoparticles (Au-NPs, UCNPs, QDs etc.),
organic polymer nanoparticles have also attracted many atten-
tions.[81] Li and coworkers demonstrated two-photon photo-
switching and two-photon photoluminescence of Spiropyran
(SP)/Merocyanine (MR)-nanoparticles (Figure 44).[82] Alternating
780 nm near infrared (NIR) and 488 nm visible laser pulses
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Figure 43. Photo and ion induced reversible aggregation of Au-NPs
modified with 52.
imparted two-photon and one-photon excitations, respectively.
The two-photon process triggered switching of the SP-nanopar-
ticles to MC-nanoparticles as well as the fluorescence emission.
The one-photon process, however, photo-switched the MC-nano-
particles back to SP-nanoparticles. Since UV or near-UV light is
not preferred in cellular imaging, two-photon excitations of SP-
nanoparticles are expected to broaden the applications of photo-
switchable nanoparticles in advanced bioimaging.
4. Conclusion and Outlook
Definitely, photochromic materials are very promising and
potential in several scientific research fields, ranging from
chemistry, physics and materials science to biology and nan-
otechnology. Nowadays, most efforts have been devoted to the
construction of functional materials with photo-switchable
fragments. Dithienylethene derivatives, unlike other photo-
switchable molecules such as azobenzene, performs negligible
steric or geometrical changes while displays large variations in
conjugation length upon photo-isomerization. This provides
a wide utility in modulating optical and electronic coupling
properties (e.g. energy transfer, donor-acceptor, conductivity,
catalysis, metal-complexation etc.) of multi-component func-
tional systems attached with dithienylethene photochromes. So
far, a large variety of molecular data storage systems, molecular
gates, molecular wires, non-linear photo switches and photo-
controlled catalyst based on dithienylethene photo-switches
have been reported.[18–23,25,48–53,83] Spiropyran, as another major
photochromic compound, offers a unique feature of signifi-
cantly increased dipole moment after photo-isomerized from
ring-closed spiropyran form to ring-open charge-separated zwit-
terionic merocyanine form. Generally, this distinctive feature
has been utilized in controlling the electro-static interactions
Adv. Mater. 2012,
DOI: 10.1002/adma.201201521

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Figure 44. Single-Photon photoswitching and fluorescence excitation contrasted with Two-Photon photoswitching and fluorescence excitation of SP/
MC-containing nanoparticles.
between spiropyran units and charged entities (e.g. charged
nanoparticles and metal ions), both in bulk solution[79] and
modified surfaces.[72b,74d] Azobenzene, another shining star of
photochromic family, also plays an important role in photo-mod-
ulated electro/optic devices,[62b,84a–84b] photo-switchable surface
and nanostructures,[7a,7c,84c−84f ] and photo-triggered biological
applications[84g−84j] due to its significant steric or geometrical
changes by light stimulation. Recently, azobenzene derivatives
have been widely reviewed in various research fields.[14b,62a,85]
Although a large step forward has been taken in this pho-
tochromic materials field, there are still several key challenges
remaining to be resolved. One of the major challenges toward
dithienylethene photochromic materials is the photoisomeri-
zation efficiency which affects not only the photochrome itself
but also the whole photo-functional entity. Despite of recent
researches on enhancing the photo-cyclization reaction (open
to closed form) efficiency by hydrogen-bonding and changing
photochromic units (e.g., substitution of thiophenes with thia-
zoles),[86] the photon quantum yield of photo-reversion reaction
(closed to open form) still remains to be especially low (usu-
ally <10%) and seldom studied. Irradiation with light in visible
or infrared region is another research focus. Using visible or
infrared light as photo-stimuli provides great opportunities in
non-destructive data writing/reading, remote controlling, cost
reduction and safe operation. Recently, a lot of innovation works
based on multi-photon technology as well as up-conversion
nanoparticles (UCNPs) have been reported.[6,26–27,77,82] However,
it’s still in its infancy. Several aspects, for instance, the design
of functional materials, the improvement of light efficiency as
well as extensive application still need further optimization.
Increasing the versatility of photochromic family with newly
invented photochromores is another important issue. Though
various photochromic derivatives were synthesized,[19–21,53,87]
brand-new type of photochromore was scarcely reported over the
Adv. Mater. 2012, © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/adma.201201521
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REVIEW
past decade. In addition, it is urgent to design sensors based on
dithienylethene derivatives accompanied by the large wavelength
shift of spectra in both open-ring and closed-ring forms when
sensing is proceeding, and such spectral changes are considered
as the reconfirmation of the photochromism. To further develop
photochromic compounds into future applicable advanced
materials, it is always desirable to improve the thermal stability
and fatigue resistance of organic photochromic materials, by
which organic materials are plagued all along. Other properties,
e.g. the ON/OFF ratio and response time which are essential
for real-time applications in organic electronic, should also be
taken in account in future researches and developments. Last
but not the least, the maintenance of photochromism on surface
materials is a main challenge in practical applications. In many
cases, the photon efficiency and reversibility of photochromic
reaction would be reduced or even lost after being attached to
the surfaces, generally metallic surfaces.[88] This problem might
be alleviated by proper design of linkage molecules or switching
to other surfaces such as silicon, graphene and semiconductors.
Taking into account of their present achievements and prob-
lems yet to be improved, photochromic materials still show a
great potential and bright future in the area of advanced func-
tional materials. The dynamic and exciting progress in the past
decade has laid a solid foundation for future applications of
novel functional materials.
Acknowledgements
This work has been supported by NSFC/China (21190033), National
Basic Research 973 Program (2011CB8068400). Thanks are extended to
all co-workers working on photochromic materials in our lab.
Received: April 17, 2012
Published online:
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