Photochromic Fluorescence Switching From Diarylethenes and Its Applications

Journal of Photochemistry and Photobiology C: Photochemistry Reviews 10 (2009) 111129
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Journal of Photochemistry and Photobiology C: Photochemistry Reviews

journal homepage: www.elsevier.com/locate/jphotochemrev
Review
Photochromic uorescence switching from diarylethenes and its applications

Chijung Yun, Jungmok You, Jeonghun Kim, June Huh, Eunkyoung Kim
Department of Chemical and Biomolecular Engineering, Yonsei University, 262 Seongsanno, Seodaemun-gu, 120-749 Seoul, Republic of Korea
a r t i c l e
i n f o
a b s t r a c t
The review describes the photochromic and uorescent characteristics of various diarylethene (DAET) derivatives, and presents recent research into their applications. This comprises a discussion of the optical characteristics of some DAET-based molecules exhibiting red, green, or blue (RGB) colors or uorescence. Molecular calculations of the optical properties of DAET interpret intriguing experimental observations and predict photochemical or photophysical properties. In particular, stabilization of HOMO in the BTFOn (n = 1, 2, 3, 4) increases the energy difference between the HOMO and the LUMO, which leads to the blueshift of absorption and emission bands as the number of oxygen attached to sulfur (n) increases. Various devices and application studies have been designed as photon-mode systems based on photochemical control of the uorescence energy. The photochromic DAET materials have shown promise as optical data storage, switching devices, and biological applications such as the development of biomaterial sensors, analysis of biological dynamics, and live cell imaging. 2009 Elsevier B.V. All rights reserved.
Article history: Received 2 December 2008 Received in revised form 14 May 2009 Accepted 22 May 2009 Available online 22 July 2009 Keywords: Photochromism Diarylethene Photoswitching Fluorescence Optical memory Bioapplications
Contents 1. 2. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Optical properties of diarylethene derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. RGB color of diarylethene derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Fluorescence of diarylethene derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3. Photo-induced reversible uorescence switching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4. Quantum chemical approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Photochromic recording and uorescence reading for optical memory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Biological applications of uorescent DAETs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112 112 112 114 118 120 123 123 125 128 128 128
3.
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Chijung Yun received his B.S. (2007) degree in chemistry from Yonsei University in Seoul (Korea). He is a Ph.D. course student at the Department of Chemical and Biomolecular Engineering in Yonsei University, working under the guidance of Prof. Eunkyoung Kim. He studies the synthesis, switching properties, and application of the photochromic materials for organic electronics.
Jungmok You received his B.S. degree (2004) in bioengineering from Yonsei University in Seoul (Korea). He is currently a Ph.D. student at the Department of Chemical and Biomolecular Engineering, Yonsei University, working under the guidance of Prof. Eunkyoung Kim. He studies the synthesis of uorescent polymers and their application to cell engineering, sensors, and soft electronics.
Corresponding author. E-mail address: eunkim@yonsei.ac.kr (E. Kim). 1389-5567/$20.00 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.jphotochemrev.2009.05.002
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C. Yun et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 10 (2009) 111129 Jeonghun Kim received his B.S. (2007) from the Department of Chemical and Biomolecular Engineering in Yonsei University. He is currently a Ph.D. student at the Department of Chemical and Biomolecular Engineering in Yonsei University, working under the supervision of Prof. Eunkyoung Kim. He studies functional photopolymers for holographic recording and 3D patterning, and their applications.
June Huh received his B.S. (1990) and M.S. (1992) degrees from Seoul National University in Korea and his Ph.D. (1998) in theoretical polymer physics from University of Groningen in the Netherlands. He was a postdoctoral research fellow at the University of Pittsburgh in USA (19982000) and joined School of Materials Science & Engineering, Seoul National University as a research professor. In 2008, he moved to APCPI, Yonsei University as a research professor, working under Prof. Eunkyoung Kim. His recent interest is theoretical modeling of patterned photoactive materials and their applications.
Scheme 1. The photochromic conversion structures of diarylethene by UV and visible light.
Eunkyoung Kim received her B.S. degree in chemistry from Yonsei University in Seoul (Korea), a masters degree in chemistry from Seoul National University in Seoul, and Ph.D. in chemistry from University of Houston. She worked for Korea Research Institute of Chemical Technology in Daejeon (KRICT) from 1992 to 2004. Since 2004, she has been a professor of the Department of Chemical and Bimolecular Engineering at Yonsei University, Seoul, Korea. Her work has primarily focused on the synthesis and patterning of functional polymers including chromogenic polymers, conducting polymers, and photopolymers. Prof. Kim has been the director of the Innovation Cluster for Bio-Fusion Industry based on Nanotechnology (ICBIN) since 2006 and director of the Active Polymer Center for Pattern Integration (APCPI), an Engineering Research Center of excellence, since 2008.
1. Introduction Interest in stimuli-responsive materials has grown rapidly due to a number of exciting applications in both bioengineering and information technology [14]. In particular, photochromism [57] offers a convenient route to the development of not only molecular photonics but also more integrated technologies, thus providing a general platform for the design of various types of photoactive device [8,9]. Photochromism is dened as a reversible transformation of a chemical species induced in one or both directions by absorption of light between two forms, A (before) and B (after), having different absorption spectra [10]. In general, photochromism can be described as a reversible change of color upon exposure to light. Such color changes in organic photochromophores are typically originated from the changes in -electron conjugation length through the molecule, to convert a colorless form (A) to a colored form (B) upon photoirradiation: A
1 2 or
(1)
The color changes are the most well-known performance of photochromic molecules. Addition to the color changes, other properties, such as conductivity [11], refraction [1217], geometrical structures [18,19], chirallity [20,21], and solubility [22] are changed. Diarylethenes are eminent of photochromic materials and undergo reversible structural change between an open (colorless) and a closed form (colored) by light [5,6,2326]. Diarylethenes (DAETs) are increasingly chosen as the preferred photochromic molecule due to their high fatigue resistance and thermal stability, which are essential prerequisites in many applications, including the manipulation of optical storage or switching devices [26,27]. A colorless open form of DAET (1o in Scheme 1)
can undergo cyclization in a conrotatory fashion to a colored form (1c in Scheme 1) upon UV irradiation. The thermal back-reaction is symmetry-forbidden, giving good thermal stability to the closed form. The reverse transition from the closed form to the open form occurs only by irradiating the open form with a visible light. These properties render DAETs suitable for a number of exciting potential applications, particularly the development of non-traditional memories and switches [8]. A distinguished example is provided by photochromic optical memories based on a photon-mode recording method, in which photophysical property changes such as transmittance or reection are exploited as a means of data storage. Because it allows recording of multiple optical properties (e.g., wavelength, polarization, and phase), the photon-mode method is advantageous in many respects over conventional heat-mode recording used in traditional optical memories in magneto-optic or phase-change recording systems [2629]. Addition to the primary color change, the photostimulation of DAETs can also modulate other properties, such as electronic characteristics, refractive indices, and uorescence [18,19,22,2839]. In particular, uorescent modulation associated with isomerization of DAETs is regarded as a promising means to achieve non-destructive readouts and security recordings [40]. An ideal candidate molecule for such a purpose should possess the ability to turn uorescence on or off by photostimulation, without induction of ring opening or ring closure reaction, However, this is difcult to achieve because the photostimulation excitation occurs in the absorption range of either open or closed form of the DAET, resulting in undesirable competition between the ring closure or opening, respectively, and uorescence. Moreover, since DAETs in most cases do not show strong uorescence, they are modied by substituting a uorophore such as anthracene, 2,4,5-triphenylimidazole, diporphyrin, or a tungsten complex [4145]. The need to optimize molecular properties and to satisfy the requirements of specic applications thus poses challenges in the design of uorescent DAETs. The present review aims to describe the photochromic and uorescent characteristics of various DAET derivatives, and to present recent research into their applications. The review is organized as follows. Section 2 comprises a discussion of the optical characteristics of some DAET-based molecules exhibiting red, green, or blue (RGB) colors or uorescence. Molecular calculations of the optical properties for DAETs are followed. In Section 3, some examples of the applications of uorescent DAETs are presented. We conclude the review by summarizing some of the important properties of uorescent DAETs and their limitations in potential applications. 2. Optical properties of diarylethene derivatives 2.1. RGB color of diarylethene derivatives DAET molecules, consisting of two electron-donating aryl groups anking a central ethene acceptor, undergo photochemical switching between open and closed forms. The open form of DAET has two different conformations, parallel conformation (P) and anti-parallel conformation (AP) [4649]. The photocyclization
C. Yun et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 10 (2009) 111129 Table 1 Structure of some diarylethene (DAET) derivatives and their photochromic color change. Diarylethene derivatives and formal diarylethene Structure Color change Reference
113
1,2-Bis(2-methyl-1-benzo[b]thiophen-3-yl) peruorocyclopentene
Colorless red
[50]
1,2-Bis(3-thienyl) peruorocyclopentene
Colorless red
[51]
3,4-Ethylenedioxythiophene (EDOT) derivatives
Colorless blue (3), blue (4)
[66]
Sulfone derivatives
Colorless yellow
[67,68]
DAET polymer derivatives
Colorless red
[70]
Oxidized DAET polymer derivatives
Colorless green
[71]
reaction can proceed only from the anti-parallel conformation. The open form (AP and P) lacks extensive electron delocalization over the central double bond and the absorption maximum is in the UV range. Conversely, ring closure leads to a conjugated planar structure in which the absorption maximum extends into the visible range of the spectrum. The open form is colorless or weakly colored in general, whereas the closed form is colored yellow, red, green,
or blue depending on the substituents. Table 1 lists representative DAET derivatives showing various colors. Benzothiophenes have been popular as electron-donating aryl groups [5255] in DAETs, because these groups give derivatives that display high quantum yields and a rapid response, as well as the high thermal stability and photostability necessary for use as molecular switches. Furthermore, the benzothiophene
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derivatives [5662] provide greater structural variation than the thiophene derivatives. Substitution of the benzothiophene units at the 2- and 2 -positions affects solubility, color, and stability of the DAET derivatives. On the other hands, the 11- and 11 positions of the benzothiophenes and the 5- and 5-positions of the thiophenes inuence coloration efciency [6364]. An electron donating or electron-withdrawing group at these positions leads to a bathochromic shift and high extinction coefcient in the closed form, as in, for example, compounds 3 and 4 in Table 1. Oxidation of the thiophene sulfur atoms to the corresponding sulfoxide or sulfone resulted in a blue-shift of absorption in the closed form (compounds 58) [6571]. In DAET polymers, electron delocalization in the closed form may be extended over the polymeric backbone; thus, absorption is signicantly redshifted (compounds 910). Most of the thiophene derivatives (bisthienylethenes, BTE, 2) [72], are substituted at the 4- and 4 -positions, as a photodecomposition often occurs to produce a photostable by-product when these positions are unsubstituted [64,73]. The ethene acceptor portion of DAETs consists of electron-withdrawing groups such as peruorocyclopentene, maleic anhydride, dicyanoethene, or perhydrocyclopentene. The peruorocyclopentene derivatives in particular have been extensively studied, as they show enhanced stability and high coloration efciency. When substituted with a series of electron-donating or electronwithdrawing groups, the closed form of DAETs display a red, blue, or green color depending on the substituent. Fig. 1 shows the photochromic color change of DAET molecules substituted with various R groups. The absorption maxima and the molar absorption coefcients of the compounds 11, 12, and 13 increase with increasing electron-donating ability of the R group. Electron-withdrawing substituents such as formyl and cyano group (compounds 14 and 15) shifted the absorption maxima to longer wavelength, but the molar absorption coefcients did not increase [74]. 2.2. Fluorescence of diarylethene derivatives Designing a DAET molecule capable of both photochromic and uorescence switching is an appealing goal that in principle may be achieved by optimizing the proportion of conformersthe socalled anti-parallel and parallel conformersin the open state [48]. Scheme 2 shows the parallel and anti-parallel conformers of the DAET molecule. However, creation of a dual-switchable molecule using this strategy is usually unsuccessful because photocyclization to a colored state occurs only from the anti-parallel conformation of the open form, whereas it is the corresponding parallel conformer that shows uorescence, albeit weak. Therefore, there is a tradeoff between photochromic quantum yield and uorescence quantum
Fig. 1. Color changes of thiophenyl DAETs 1115 upon alternating irradiation with UVvis light in hexane [74].
Scheme 2. Interconversion of parallel and anti-parallel conformers in 2.
yield. Indeed, according to the extensive studies on various DAET molecules undertaken by our research group, the uorescent quantum yield is below 5% even in a system optimally populated with the parallel conformer [75].
Scheme 3. . Synthetic route to alternating DAET oligomer, where R includes H, TMS, or alkoxy in the 1 and 4 positions, etc. [46,76].
115
Fig. 2. Absorption spectra of 17 (solid line), 1 (dotted line), and 18 (dashed line) in (a) the open form, and (b) the closed form at a concentration of 1 105 M in chloroform [46].
As an alternative approach to the creation of photochromic and uorescent DAET molecules, several reports have employed chemical combination of a DAET with a uorophore, or simply a doping method. Introduction of a uorophore often results in a high uorescent quantum yield but low photochromic efciency [45], since introduction of the uorophore into the DAET changes the ground or excited electronic states to favor the parallel conformer. Therefore, an important goal has been to design a photochromic molecule that incorporates a uorophore while maintaining the anti-parallel conformation; such a species should give high uorescent quantum yield while maintaining high photochromic conversion efciency. To investigate the above hypothesis, the uorophore pphenylenevinylene (PPV) was introduced through a Wittig polycondensation reaction to generate a highly uorescent copolymer (compound 17 in Scheme 3) [76]. The copolymer was synthesized from aldehyde-substituted 1,2-bis(6-formyl2-methylbenzo[b]thiophene-3-yl)hexauorocyclopentene (compound 16) and the phosphonium salt made from 1,4bis(triphenylphosphonionmethyl)benzene dibromide. This synthetic scheme was applied not only to benzo[b]thiophene but also to thiophene derivatives, and the PPV units in the copolymer were also modied with various groups to improve solubility or the photochromic and uorescent properties. Fig. 2 shows the absorption spectrum of compound 17 in CHCl3 obtained upon UV irradiation, compared with the spectra of compounds 1 and 18. Upon exposure to 325 nm light, the colorless solution of compound 17 changed to deep red, and showed new absorption bands at 381 and 555 nm, characteristic for the closed isomer. The red color indicated formation of the closed form of the compound 17. After irradiation with a visible light (>540 nm), the
red color was bleached to colorless, indicating reversion to the open form of compound 17. The absorption maxima ( max ) of the open and closed forms of compound 17 were observed at 339 and 555 nm, respectively, showing a shift toward longer wavelength compared with max for the monomeric compounds 1 and 18. These results indicate that the singlet excited states of both the open and closed forms of compound 17 were signicantly stabilized compared to those in the monomeric compounds, possibly due to increased -electron delocalization. Compound 17 shows an improved quantum yield of photocyclization (0.38) because the rigid and planar DAET structure directly connected to PPV units favors the anti-parallel conformation in the diarylethene unit. Compound 17 showed very strong uorescence because of the PPV unit. As shown in Fig. 3, the uorescence of the solution before UV light irradiation is 10 times stronger than that of the solution after UV light irradiation due that the uorescence intensity decreased with decreasing the open form upon irradiation with UV light. Interestingly, the solution after UV light irradiation, to generate closed form, showed very weak uorescence intensity because the absorption energy of the closed form is used for ring opening and non-radiative process [77,78]. This indicates that uorescence may be controlled by photochromic conversion of DAET [77,78]. Such photochromism/uorescence switching in BTFPPV (compound 17) could be applied to the development of non-destructive optical recording and reading systems by exploiting the difference in uorescence between the photochromic and non-photochromic sites. Fig. 4 shows the uorescence and photochromism of the open form of compound 17 [46]. Both the photochromic color change
Fig. 3. Fluorescence emission spectra of 1 (a), 18 (b), and 17 (c) before UV irradiation (excitation source for emission spectrum: i, max of the open form) and after UV irradiation (iiiv) (excitation source for emission spectrum: max of the closed form in UV region (ii and iv) and that in visible region (iii)) [46].
116
Fig. 4. Photographs of a solution of 17 (1 104 M in chloroform). (a) Under UV irradiation in a dark room, (b) before UV irradiation under room light, and (c) after UV irradiation under room light [46].
Fig. 5. The photophysical process in diarylethenes substituted with a uorophore.
and the uorescence were affected by functional groups in the PPV side chain as well as the structure of the DAET unit. Due to signicant delocalization of -electrons along the polymer backbone. The oxidation potential and ionization potential of the closed form of 17 are much lower than that of the open form of compound 17. Thus photocurrent generation was observed in the thin lm derived from the closed form of compound 17 [76]. Therefore, in this case both uorescence and photocurrent switching accompany the photochromic switching, which can be controlled by light as described below. Fig. 5 illustrates the photofunctional process in the DAET polymer 17 [76]. The DAET units are excited to a singlet state by absorption of light at wavelength 1 . Molecules in the excited state undergo one of the four major processes: (1) return to the ground state open form with concomitant uorescent emission of light, (2) isomerization to the closed form without light emission, (3)
charge separation to generate a photocurrent, or (4) non-radiative process. All four processes are inter-related and the efciency is highly dependent on the lifetimes of the excited states. On the other hand, when the DAET polymer is exposed to light at wavelength 2 , uorescence is induced but photochromic isomerization does not occur. Therefore, photochromic conversion and uorescence can be controlled by tuning the wavelength of the excitation light. A photochromic and uorescent compound 19 has been synthesized using photochromic DAET, an adamantyl spacer, and the extensively studied uorophore anthracene [8,79]. This study demonstrated that digital uorescence switching by the DAET molecules in 19 could be controlled by irradiation with ultraviolet and visible light at the single-molecule level, as shown in Fig. 6. DAETs containing benzothiophene groups have generated considerable interest due to their thermal stability and fatigue resistance; however, these DAETs show rather small photochromic uorescence changes, and have therefore generally been monitored by UVvis absorption spectroscopy [50,80]. Because monitoring changes in absorption is not a viable method for reading stored data because of signal interference, other methods were adopted to achieve a non-destructive readout. These include observation of changes in optical rotation, refractive index, uorescence, and IR spectra [22,42,47,48,52,82]. In particular, uorescence changes upon photochromism are promising in the development of a nondestructive optical readout, because of single-molecule sensitivity. The DAET derivatives showed strong uorescence in the open form. The uorescence energy of the open form lies between the absorption energies of the open and closed forms, resulting in uorescence energy transfer from the open to the closed form, and excitation of the latter and its conversion to the open form. The implication of this nding is as follows: data can be recorded by photochromic conversion, but subsequently erased as uorescence energy is transferred from the open form to the closed form during data reading. Thus, high uorescence is necessary in the closed form that does not interfere with emission energy of the open form or with absorption of the closed form. To design a molecule with the desired spectral characteristics, we modied a DAET to a highly stable oxidized form that requires high absorption energy. DAETs were oxidized at sulfur to give sulfoxides and sulfones, as shown in Scheme 4. The degree of DAET oxidation could be controlled by varying the content of the oxidizing agent, mchloroperbenzoic acid (mCPBA). For example, as shown, both sulfur atoms in compound 1 were oxidized to sulfoxides in the presence of excess mCPBA. By changing the oxidation level, it was possible to control the uorescent and photochromic properties [67,83]. The absorption maxima of the closed forms of the oxidized DAETs were blue-shifted, indicating that the oxidized DAETs require high absorption energy. As shown in Fig. 7(b), the oxidized acetylsubstituted compound 21 was yellow colored in the closed state. Interestingly, compound 21 showed stronger uorescence in the closed form than in the open form (Fig. 7b); the same phenomenon was observed with compound 20 [68]. Fluorescence switching of compound 21 was more reproducible and displayed higher uorescence contrast than that of the unsubstituted analog 5. An additional advantage of these oxidized compounds is that their
Fig. 6. Structure of the open and closed states of DAET derivatives in which a photochromic DAET derivative is linked to a uorescent anthracene derivative through an adamantyl spacer [8,79].
117
Scheme 4. Oxidation of compound 1 [67,83].
Fig. 7. (a) Photochromic reaction of DAET derivatives. (b) Photographs of solutions of compound 21 (1.0 104 M in ethyl acetate): (a ) color of o-DABTFO4 (21o before UV irradiation under room light, (b ) c-DABTFO4 (21c, yellow in photostationary state after UV irradiation), (c ) uorescence of 21o (weak emission) after photo-excitation with a 365 nm UV lamp and (d ) uorescence of c-DABTFO4 (21c green emission). Color and uorescence of 21 are compared with those of 20o and 20c (bottom, weak emission), respectively [68].
structure endows them with superior fatigue resistance compared with the corresponding un-oxidized molecules. The oxidized, polymeric poly-BTFO4 (compound 10) was synthesized from compound 5 via FriedelCrafts alkylation [84]. Compound 10 showed 6-times-higher uorescence contrast upon irradiation with UVvis light than the monomeric BTFO4 (compound 5); vivid uorescence was observed as shown in Fig. 8. The solubility of polymer 10 in organic solvents allowed for its processing into a photochromic, uorescent thin lm that could be utilized in a photoswitching system. The closed forms of these oxidized DAETs gave a uorescence band at longer wavelength than the corresponding absorption band. Therefore, uorescence energy transfer from the excited states to the closed form is unlikely. This is important in the development of a non-destructive optical reading system, as described above. Furthermore, the uorescence intensities of the closed forms of both compounds 5 and 10 were much higher than those of the corresponding open forms [71]. The uorescence quantum yields of the compounds 5c and 10c were determined to be 0.011 and 0.093, respectively, using 3-aminouoranthene in cyclohexane as a reference. This result indicates that the uorescence of closed compound 5c is amplied by polymerization. The monomeric units of the compound 5 are linked by a methylene spacer (CH2 ), which may prevent approach of the rigid BTF4 units in the polymer chains, thereby diminishing non-radiative decay processes.
Scheme 5. . Molecular structures and photochromism of oxidized derivatives of bis(2-thienyl)ethenes.
The oxidation of DAETs was extended to the preparation of sulfoxide derivatives of thienylethenes [84], as shown in Scheme 5. As shown in Fig. 9, the oxidized compound 2 derivatives displayed photochromism at wavelengths that varied depending on the substitutents. Compound 22 showed a spectral change within the visible region, whereas compound 23 showed invisible photochromism [84], a property that could be exploited for the development of opto- and electro-molecular devices to be used under ambient light. The quantum yield of the cyclization reaction of compound 22o is much lower than that of compound 23o; the low yield of the ring-opened isomer compound 22o may be
Fig. 8. Change in uorescent intensity by the polymerization of 510 [71].
118
Fig. 9. (a) Absorption spectra in 1,4-dioxane solution: 22o (solid line), the photostationary state of 22o under irradiation with 430 nm light (short dash line), and 22c (large dash line). Inset: photographs of a solution of 22 and the photostationary state (PSS) upon irradiation with 430 nm light. (b) Absorption spectra in 1,4-dioxane solution: compound 23o (solid line), the photostationary state of 23 under irradiation with 390 nm light (short dash line), and 23c (large dash line). Inset: photographs of a solution of 23 and the photostationary state (PSS) upon irradiation with 390 nm light [84]. [Original citation]-Reproduced by permission of the Royal Society of Chemistry. http://dx.doi.org/10.1039/b804137g.
Scheme 6. Fluorescent photoswitching molecules comprising a photochromic DAET and (a) perylene bisimide uorophore, or (b) bis(phenylethynyl)anthracene uorophore.
attributed to extended -conjugation. Table 2 summarizes the uorescence properties of the DAET derivatives. 2.3. Photo-induced reversible uorescence switching Photochromism in DAETs is a reversible transformation between open and closed chemical states, as discussed above. These two states have different absorption and emission spectra, allowing photons to induce reversible switching from one state to the other [79]. The photo-induced uorescence switching contrast ( F ) between the two states is estimated from the uorescence intensity ratio between the uorescent and non-uorescent states. BTFO4 (compound 5) and the corresponding polymer 10 display reversible on/off uorescence switching, as shown in Fig. 10. The uorescence quantum yield of compound 10 was much higher than that of the compound 5; thus, the compound 10 displayed more efcient uorescence switching than the compound 5 [83]. The F values for compound 10 and 5 were estimated to be 55 and 9, respectively, based on the switching data in Fig. 10. Fluorescence switching was also reported for DAETs linked to a uorophore through an adamantyl spacer (Scheme 6). Although the uorescence intensity upon irradiation with UV and visible light in solution was gradually changed, digital on/off switching between two discrete states was observed at the single-molecule level [89]. Photo-induced uorescence switching was also observed in DAETs linked with the uorophore 4-amino-N-methylphthalimide, such as compound 30 shown in Fig. 11. The F value was estimated as 1.5 from Fig. 11(b). It is noteworthy that the emission maxima of the compound 30 showed a positive solvatochromic effect [90]. Furthermore, the uorescence quantum yield of the compound 30 decreased as solvent polarity increased from cyclohexane to dioxane. A new unsymmetric diarylethene derivative, 1-{4-(5-methoxy2-(2-pyridyl)thiazolyl)}-2-{3-(2-methylbenzo-[b]thiophenyl)}
hexauorocyclopentene (compound 31) was reported to show photo-induced uorescence switching [91]. Fluorescence behaviors of the compound 31c could be multiply switched through various reaction such as protonation, coordination, and photochemical reactions, due to the existence of multiple binding sites. A uorescent molecular switch (FMS) was explored with DAET and rhodamine uorescent dye, which are linked through aspartic acid (compound 32) [92]. The reactive group in this FMS, Nhydroxysuccinimide ester (NHS) allows selective labeling of amino containing molecules or other materials. In ethanol solutions, the compound displays a large uorescent quantum yield of 52% and a
Fig. 10. The uorescence switching of compound 5 (open circles, excitation 398, emission 492 nm) as compared to 10 (closed circles, excitation 412, emission 505 nm) in ethyl acetate (1.0 105 M) upon alternative illumination with 312 nm (solid line) and visible light (dashed line) [71].
C. Yun et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 10 (2009) 111129 Table 2 Photochromic and uorescence properties of DAET derivatives. Structure Photochromic color (nm) Fluorescence color (nm) Fluorescence quantum yield Reference
119
412, Violet
505, Green
0.093a (in cyclohexane)
[71]
398, Violet
530, Light green
0.01a (in cyclohexane)
[83]
500, Light blue
620, 523, 561
[85]
555, Dark blue
450, Blue
0.38 (in hexane)
[76]
560, Green
640, Red
0.40 (in hexane)
[86,87]
574, Dark blue
720, Red
0.36 (in hexane)
[88]
680, Red
464, Blue
[91]
Ref. 3-Aminouoranthene (QY = 0.53 in cyclohexane).
large uorescence modulation ratio (94%) between the two states that may be interconverted with visible and near-UV light. The rhodamine-101 (Rh) linked DAET could be encapsulated inside a silica nanoparticle (NP). Fig. 12(a) shows a chemical structure of the uorescent molecular switch and the photochromic reaction responsible for the uorescence modulation. A high switching contrast was achieved
by tuning the absorption and emission properties of the building blocks so that only one of the isomers of the DAET is highly efcient as an energy acceptor. The silica particles of compound 32 show 30 successive switching cycles (UV/red light) as determined by a confocal microscope on a single silica particle. These results indicate that the NP uorescence could be repeatedly modulated with UV and visible light.
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Fig. 11. (a) Structure of 30c. (b) Photoswitching of 30 in cyclohexane. Absorption and emission are plotted as a function of the irradiation time during the complete rst cycle, and then only in the photostationary states after irradiation with UV (circles) and visible light (squares) [90]. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission.
2.4. Quantum chemical approaches A number of experimental approaches have sought to synthesize novel DAET-based molecules and other molecular scaffolds intended to show improved performance in specic applications. In addition, many quantum chemical (QC) approaches based on ab initio or semi-empirical calculations have been performed, either to interpret intriguing experimental observations or to predict photochemical or photophysical properties. These computational approaches are not only important in their own right for testing the validity of a given model but also valuable for the design of molecules having desirable photoactive properties. Earlier computational investigations of DAET-based molecules have concentrated largely on cyclization or cycloreversion reaction pathways using various QC approaches: modied neglect of differential overlap (MNDO) [93], complete active space self-consistent eld/complete active space perturbation theory (CASSCF/CASSPT2) [9497], HartreeFock (HF) [98], or density functional theory (DFT) [5358]. These methods pinpoint the detailed reaction pathway and rationalize basic properties of DAETs (e.g., thermal stability, quantum yield, and cyclization/cycloreversion dynamics) [99102]. From those computational search over the potential energy surfaces of ground and excited states along the reaction coordinate, between the open and closed state, it is suggested that the overall reaction pathway of both cyclization and cycloreversion is a series of linked states: a populated 1B excited state (Franck Condon state), followed by relaxation to the doubly excited 2A state, and subsequent relaxation to the 1A ground state via conical intersections (2A/1A CI), which are the gateways for the cyclization/cycloreversion process in the potential energy surfaces.
Particularly, a detailed investigation of the potential energy surface revealed that the energy of 2A/1A CI in the open form is larger than that in the closed form, which explains the experimental observation that the quantum yields of cycloreversion are smaller than those of cyclization [96]. A schematic reaction mechanism is shown in Fig. 13 where the locations of ground states (1A), S1 excited states (2A), S2 excite states (1B), and CIs as well as plausible reaction paths are indicated in a schematic energy landscape. Clearly, this suggests that the primary factor determining quantum yields of cyclization/cycloreversion is the energy difference between the two conical intersections of 2A/1A CI-O and 2A/1A CI-C, which can be used for a guideline to design a DAET with optimal quantum yields. Various theoretical models have also been tested on DAET derivatives for their ability to predict electronic spectra, which are essential in designing photochromic DAETs [101,103107]. In particular, the prediction of absorption spectra is of special importance as the rst step in the design of a tailor-made DAET with the desired photochromic characteristics. The absorption maxima for DAETs correspond to an electronic transition resulting primarily from promotion of an electron from the HOMO to the LUMO. These frontier orbitals can provide us with additional information about the contributions of substituents in a DAET molecule to the electronic absorption. As examples, the HOMO and LUMO for basic closed-state DAET skeletons bearing peruorocyclopentene (BTF6, BTFO1, BTFO2 and BTFO4) are depicted in Fig. 14. The HOMOs for all the compounds at closed state are located in the vicinity of the -conjugated fragments in the hexadiene and in the benzothiophenes ring, while the LUMOs are found mainly on the CC bonds in the center and the periphery of the hexadi-
Fig. 12. (a) Chemical structure of the uorescent molecular switch rhodamine (Rh)aspartic acid (AA)diheteroarylethene (DAE) and the photochromic reaction responsible for the uorescence switching. The uorophore moiety is excited with green light: red light is emitted in the on state, while resonant energy transfer (RET) prevents this emission in the off state. (b) Series of 30 successive complete irradiation cycles (UVvis light) performed on a single silica particle in a confocal microscope [92]. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission.
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Fig. 13. Schematic representation of reaction pathway of DAET [94]. The following abbreviations are used to represent each state. FC: Franck Condon states; C: closed form; O: open form. The X/Y CI-Z stands for the conical intersection between X and Y states in the Z-form. The solid lines represent plausible reaction pathways after an excitation of the ground state in the closed form (1AC) while the dotted lines represent the pathways after an excitation of 1AO. The pathway represented by grey lines is less plausible than that by black lines because of large structural dissimilarity (i.e., large separation in the reaction coordinate).
ene, and partly at certain locations in the peripheral phenyl rings. Locations of the HOMO and LUMO are affected more markedly by replacement of sulfur atoms in the benzothiophenes when the sulfur atom is oxidized to sulfoxide group. The same trend is seen in the HOMO of the compound 7. In the case of the compound 5 where two oxygen atoms are attached to each sulfur atom of the benzothiophene rings, it is likely that only a very slight electron density remained on the sulfur atoms due to a strong electrophilic nature of oxygen atom. On the other hand, no such change is observed in the LUMOs of these DAETs. Interestingly, a lone pair electron on the sulfur atom in the HOMO of 1c has an opposite sign from neighboring electrons, which suggests that nodes in the electron density should be located between sulfur and neighboring atoms. The reduction of electron density in the HOMO of the sulfur atom by oxidizing it to the sulfoxide or sulfone thus eliminates the node to stabilize the HOMO. Hence, the stabilization of HOMO in the BTFOn (n = 1,2,3,4) increases the energy difference between the HOMO and the LUMO, which require more energy for electronic transition and leads to the blue-shift of absorption bands as the number of oxygen attached to sulfur (n) increases. Table 3 lists the main geometric parameters (bond lengths and dihedral angles associated with the planarity of central hexadiene skeleton) of BTF6 (compound 1), BTFO2 (compound 7), and BTFO4 (compound 5) in the closed state optimized at B3LYP/6-31G (d) level. The atomic numbering is denoted in Table 4. The aryl hexadiene of the compounds 1 and 5 in closed form can be considered
as alternating polyenes, i.e., linked points of 9-10-11-12-5-4-3-6-6 3 -4 -5 -12 -11 -10 -9 and therefore it is very likely that -electrons is delocalized over nearly the whole molecular system. A useful reference for investigating -conjugation is that the bond length of a carbon-carbon bond under -conjugation effect should be in the range between 1.339 (unperturbed C C double bond length) and 1.540 (unperturbed CC single bond length). Note that the bond lengths of (3, 4) and (4, 5) in the thiophene ring of compound 1 are similarly 1.455 and 1.427 , respectively, whereas those of compound 5 are 1.465 and 1.411 . These geometric results show that the single bond and double bond for BTF6 are more averaged than the compound 5, suggesting stronger -conjugation effect for BTF6 in comparison with that for compound 5. Also, of interest is that the dihedral angles of (3, 6, 6 , 3 ), (5, 4, 3, 6), and (5 , 4 , 3 , 6 ) for BTF6, which can characterize the degree of planarity of diaryl hexadiene, are 10.7 , 169.1 , and 170.0 , respectively, and those for compound 5 are 12.8 , 177.5 , and 168.8 , indicating that the diaryl hexadiene in the compound 1 is more planar than that in the compound 5. Hence, these geometric results also support that the absorption wavelength of compound 1 should be longer than that of compound 5. Traditionally, the use of semi-empirical calculations to compute electronic spectra has been popular because these methods are computationally much less demanding and more easily handled than non-empirical ab initio methods. Typically, the ground-state structure is optimized by NDDO-based methods such as MNDO, AM1, and PM3, which should be systematically checked such that all vibrational frequencies are real-valued. For the evaluation of electronic spectra, the ZINDO-S methodwidely used for calculating spectroscopic propertiescan be employed with congurational interaction calculations that compute excited electronic congurations. Despite much faster computation compared with the state-of-the-art time-dependent density functional theory (TDDFT) method, semi-empirical calculations of DAET spectra have one major drawback: quantitative agreement between predicted and experimental values is relatively poor, although the predicted values for a series of DAET derivative correlates rather well with experimental values. Such discrepancies may be partly attributed to the neglect of solvent effects, but seem to arise more from a lack of validation of parameterization and the range of applicability of a given semi-empirical model. Therefore, the semi-empirical results need to be strongly corrected before being correlated with experimental results [103]. Furthermore, correlations between the predicted and experimental results are not usually extensive enough to cover all DAETs. Based on the absorption spectra data of DAETs in this review and reported in the literatures we exemplify semi-empirical calculations of DAETs in closed state. The absorption maxima ( max ) from ZINDO-S/AM1 for various DAETs are compared with experimental values in Fig. 15. The semi-empirical approach yields a smaller
Fig. 14. HOMO (bottom), LUMO (top), and the bandgap energy for BTF6, BTFO1, BTFO2, and BTFO4.
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Table 3 Main bond lengths (L) and dihedral angle (DAET) of BTF6 and BTFO4. Molecule BTF6 BTFO4 L () (C3C4) 1.455 1.465 L () (C4 C5) 1.427 1.411 DA ( ) (C3, C6, C6 , C3 ) 10.767 12.807 DA ( ) (C5, C4, C3, C6) 169.101 177.594 DA ( ) (C5 , C4 , C3 , C6 ) 170.035 168.843
max than the experimentally measured value. Nevertheless, the correlations between the calculated max , for the closed forms of various DAETs, and experimental values is reasonably good over a broad range of wavelengths ( max = 400800 nm). Interestingly, the correlations could be grouped into two different series: a group consisting only of C, H, F, and S atoms (Class I), and a group comprising N and O in addition to C, H, F, and S (Class II). Molecular structures of Class I and Class II are listed in Table 4. The max of
the DAETs in Class I by ZINDO-S/AM1 is correlated well with those of experimental values. The slope of the plot for the max of Class I by ZINDO-S/AM1 against experimental values is 0.675 while that of Class II is 0.218. Although the raw values of calculated max need to be corrected using a linear regression that signicantly will reduce the discrepancies between the calculated and experimental results, the plot in Fig. 15 could be useful for the estimation of max for a new DAET.
Table 4 Chemical structures of DAET in Class I and Class II. Structure
II
123
3. Applications Photochromic media offer several major advantages over current optical systems, for their erasable/rewritable capability, high resolution, and high sensitivity [81,82]. A photochromic conversion followed by a uorescence change can be applied to various applications for which the reversible photochromic change provides a convenient light-activated method of converting a uorescent state to a dark state. Fluorescence detection can be used in nondestructive recording and detection and bio-imaging because it requires a much lower-power light source than detection based on absorption. Here we describe two selective applications: optical recordings including holography for security lm and uorescence resonance energy transfer (FRET), and biological applications using the photon-mode uorescence switching property of DAETs. Holographic optical data storage is a unique process for achieving high-density data storage in three dimensions. FRET is a distancedependent physical process in which energy is transferred from an excited donor uorophore to an acceptor chromophore. In the area of biological applications, recent studies have explored uorescence switching and imaging by photoirradiation of photochromic DAET derivatives. 3.1. Photochromic recording and uorescence reading for optical memory The TDDFT method, which is an extension of DFT that predicts the time-evolution of electronic density, provides predictions of the absorption wavelength that are much better than those obtained using ZINDO-S/AM1. The calculation is performed using DFT exchange-correlation functionals such as popular B3LYP with a choice of Poples basis sets. Approaches based on TDDFT have been reported for relatively simple DAET structures [101,105107]. A notable study of the absorption spectra of a series of DAET derivatives using the TDDFT method suggested that 6-311+G (2d,p) and 6-311G (d,p) basis sets give the most accurate estimates of the absorption maxima; the raw estimates had a mean average error of 30 nm, and corrected estimates had a mean average error of 7 nm [106]. Similar TDDFT results were reported for peruorocyclopentene-substituted DAET derivatives [107] or maleic anhydride-substituted DAET derivatives [105] with similar error. The correlations between experimental and TDDFT results of uncorrected max for various DAETs are shown in Fig. 15. Although the DAET structures in this study were closely related, it is nevertheless clear that the errors between predicted and experimental values are much smaller and more systematic for TDDFT than those obtained using semi-empirical methods. Control of uorescence (FL) emission of DAETs has recently become important for some specic applications, particularly the development of non-destructive readout memory and bio-imaging, which impose stringent requirements on the design of DAETs. As a minimal requirement, a candidate molecule for a non-destructive readout should possess the ability to turn uorescence on or off by photostimulation, while the excitation should not induce ring opening or ring closure. This requirement could be fullled by designing new DAETs which may give high uorescence at the closed state. Stabilizing DAETs by oxidizing sulfur atoms is one method, as described for BTFO4 (compound 5) in the previous section. Despite the increasing necessity of theoretical design parameters to guide DAET synthesis, investigation and assessment of the factors affecting DAET uorescence remains at an early stage. To facilitate molecular design, future theoretical modeling should focus on FL emission dynamics as well as emission spectra, and energy and electron transfer modulation with uorophore-linked DAETs [108,109]. Port and co-workers reported a triad molecule composed of anthracene as a donor, DAET as a switching unit, and pyridinium as an acceptor (compound 58 in Scheme 7) [110]. The photochromic DAET bridge directly linked to the pyridinium acceptor was separated from the anthracene donor with a methylene -spacer, which maintains the spectroscopic identity of both the donor and the switch-acceptor. In compound 58o, excitation of the anthracene leads to intramolecular charge separation that was identied from the transient absorption spectra of the anthracene radical cation; in this open form of compound 58, uorescence was on. Conversely, in compound 58c intramolecular charge separation was suppressed, and uorescence was off. Thus, compound 58 can be used in a two-photon 3D optical data storage system based on modulation of the uorescence emission of a highly efcient uorescent dye and a photochromic DAET [111]. This system is suitable for recording data in thick storage media and provides a non-destructive readout method without exhibiting any apparent fatigue, even after 10,000 readout cycles. The storage medium consists of PMMA-co-VBP, a commercially available photochromic molecule (compound 1), and the two-photon absorbing uorine dye (2,7-bis[4-(9,9-didecyluoren2-yl)vinyl]phenylbenzothiazole) (Scheme 8). Data were stored according to the uorescence intensity increase when the uorene derivative was excited in an area where photochromic conversion was not occurring; therefore, data recording was made possible by photochromic patterning using a photomask. Z-scan signals were clearly observed as a result of exciting the closed form of DAET compound 1 at wavelengths shorter
Fig. 15. Plot of the calculated absorption maxima against experimental absorption maxima for various DAETs: the numeral at each point corresponds to the compounds listed in Table 4. All calculations were performed using Gaussian 03 program and the experimental values of are taken from Refs. [67,68,49,103].
Scheme 7. Photoisomerization of a compound 58 in the pcFRET system.
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Fig. 16. (a) Two-photon readout data and (b) intensity prole [111]. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission.
than 900 nm. The two-photon absorption constants (2PA ) of the closed form of DAET compound 1 at 680, 750, and 800 nm were 150, 145, and 120 GM, respectively. Therefore, the two-photon readout system is based on efcient readout of up-converted uorescence data, which is modulated by the ring closure/opening transformations of the photochromic material. Fig. 16(a) shows the two-photon readout data recorded by single-photon excitation. Using this non-destructive, two-photon readout method, the data were read up to 10,000 times with only a small decrease in the contrast and uorescence intensity of the original image. Setting a uorescence intensity threshold, as in Fig. 16(b), would allow this method to be used for binary data storage. In a thicker lm, the recording and reading can be executed on multiple levels, providing a non-destructive readout of 3D data [112,113]. Holographic media have been used in security applications and anti-counterfeit products. Holograms record secure digitized data in two or three dimensions that cannot be easily copied. In addition, dry-lm photopolymer composite can be modied and used for multi-functional detection in the presence of additional materials [114117]. Holographic recording on a photochromic lm affords an erasable 3D recording; however, the diffraction efciency of the photochromic lm is small (<2%) because of small refractive-index modulation (<0.0001) in response to absorbance changes. In an effort to prepare multifunctional photopolymer media, photochromic or uorescent
Scheme 8. Storage medium components. Molecular structures of the open and closed forms of the DAET 1 and the uorene derivative.
photopolymers were evaluated as holographic security media. The diarylethene derivative, 1,2-bis[6-(3,4-ethylenedioxythienyl)2-methyl-1-benzothiophen-3-yl]peruorocyclopentene (BTFTT, 4), has been examined as a photochromophore [118]. Compound 4 is colorless under visible light, but it changes to dark blue upon exposure to a UV light source as it undergoes photoisomerization (Scheme 9) [118]. The open form is uorescent but the closed form is less so. The color of the photopolymer lms containing photo-reactive monomers and compound 4 was yelloworange because of the color of the coumarin sensitizer. Before UV irradiation, the UV spectrum of the lm showed an absorption maximum at 463 nm due to the sensitizer. The photopolymer containing the chromophore gave a high diffraction efciency and fast reactivity under a holographic recording system equipped with a 491 nm laser, ensuring that holographic images could be efciently recorded on the photopolymer lm. A hologram record is shown in Fig. 17(a). Interestingly the uorescence of the photopolymer lm containing compound 4 is enhanced upon holographic recording. Thus, a uorescent mark can be stored on the lm and detected by a probe beam, as shown in Fig. 17(b). The uorescent mark was erased upon exposure to a UV light but recovered when exposed to visible light. Importantly, the photopolymer lm containing compound 4 showed photochromism, as well as uorescence switching, under a UVvis light source. Thus, the lm becomes dark under UV irradiation, hiding a secure image, as shown in Fig. 17(c). The image is recovered when the lm is exposed to a visible light. The images of the real objects were recorded on the photopolymer lm within 15 min of recording. The photographs of the images and real objects (screw and letter Y) are shown in Fig. 17(d). The holographic images were captured by a digital camera and could be detected under visible light illumination. These results suggest that photopolymer lm containing a photochromic uorescent chromophore could be applied in security media and anti-counterfeit systems. Fluorescence switching can also be applied to a two-photon 3D data storage, which uses photochromic recording and uorescence reading by a two-photon process. The quadratic dependence of twophoton absorption on the incident light intensity means that the recording and reading of data by the two-photon process has the advantage of low crosstalk between the multiple memory layers [119]. Furthermore, uorescent materials generally remain intact without decomposition during reading. The JaresErijman and Irie group reported on an optical reading/writing system based on FRET, using lucifer yellow as a electron donor and bis(thienyl)ethane as an acceptor. They found that the single-photon uorescence emission
125
Scheme 9. Photoisomerization of compound 4.
of the donor is reversibly modulated by transformation of the photochromic acceptor on irradiation with appropriate UV or visible light [27,120,121]. In a FRET system, the energy of a donor molecule is transferred to an acceptor in a non-radiative manner through a dipoledipole interaction (Scheme 10) [113]. A photochromic FRET (pcFRET) system is composed of a uorescent compound as a donor and a photochromic compound as an acceptor. As shown in Scheme 10, compound 59 comprises lucifer yellow cadaverine as donor, and a thermally stable, photochromic DAET as acceptor, linked by a covalent tether. Irradiation at 313 nm converted the DAET from the open form to the closed form, in which FRET caused uorescence to be switched off, as the absorption band of the closed form of the DAET overlapped considerably with the emission band of the donor uorophore. In the open form, the donor is not perturbed by the DAET and shows strong acceptor-free uorescence. Thus, the photochromic FRET system comprises a photoswitchable uorophore that is reversibly switched between on and off states as a result of photoisomerization of the photochromic acceptor, which changes its excitation properties. 3.2. Biological applications of uorescent DAETs Photochromic compounds showing reversible and stable switching properties have attracted much interest due to their
Fig. 17. Detection of information recorded in on the multi-functional photopolymer lm containing BTFTT for security media [113].
potential applications in photonic devices, as well as in biological analysis. In contrast to the large body of research into the application of DAETs in photonic devices, few studies have evaluated biological applications such as the development of biomaterial sensors, analysis of biological dynamics, and live cell imaging. Recently, Matsubara et al. developed a polymeric gel doped with a photochromic molecule to control gel swelling by light [122]. The gel was a copolymer of the temperature-sensitive N-isopropylacryl amide (NIPA) monomer and the light-sensitive 4-acryloylaminoazobenzene (AAB) monomer. Interestingly, this polymer gel underwent rapid two-state switching between two colors in synchrony with the transcis photoisomerization of the azobenzene moieties triggered by irradiation with light in a temperature-controlled environment. Giestas et al. reported a multistate network designed for biological monitoring composed of 4 -acetamidoavylium and 4 -aminoavylium, which were reversibly interchanged by inputs of light, pH, and heat [123]. This study introduced the basic concept of recording and reading system by photoisomerization and acid reaction. Fluorescent photoswitching molecules have been used to develop uorescent probes for metal ions in which metal coordination gives rise to a reversible change in emission intensity and emission wavelength; in one study, a photochromic thiophenecontaining DAET was linked with terpyridine units via a phenylene tether (compound 60) [124]; in another, a diarylethene Schiff base ligand was synthesized (compound 61) [125]. These systems are applicable to environmental and biological processes in which metal ions such as zinc are essential. Conventional uorescent probes such as rhodamine and cyanine dyes are widely used as uorescent probes for imaging intracellular events; however, these molecules give an irreversible response [126128]. Recently, several photoactive uorescent proteins have been developed as cellular tags and protein probes. As with the small molecules above, the on/off protein uorescence switch is controlled by light. These reagents are attractive diagnostic and biological imaging agents for study of the behavior and function of target proteins [129131]. A novel green uorescent protein (GFP), asFP595, extracted from Anemonia sulcata, behaved as a switchable uorescent marker because of the presence of photoactivable groups within the molecule [132]; however, these large uorescent proteins are generally unable to locate and bind to the target protein. Therefore, there exists a need for the development of new photoswitchable small uorescent molecules for protein labeling in cells. Table 5 presents some representative DAET derivatives developed for biological applications. The discussion focuses on the application of DAET derivatives that undergo uorescence switching triggered by photoirradiation. A new photochromic compound is reported for uorescent labeling of proteins comprising a photochromic DAET moiety, a uorescein-derived uorophore (FL), and an amine-reactive succinimidyl ester (SE) moiety (Fig. 18(a)) [133]. This DAET derivative displayed photoswitching of uorescence via intramolecular energy transfer from the uorophore to the DAET moiety. The
126
Scheme 10. Structures of the open and closed forms of 59 in pcFRET system.
uorescence of the DAET derivative is efciently quenched upon photocyclization because of the spectral overlap of the absorption band of the closed-form acceptor with the emission band of the FL unit as donor. Therefore, this DAET-FL-SE compound represents a protein labeling reagent in which uorescence switching following attachment to the target protein may be controlled via the photoreaction shown in Fig. 18(b). Fig. 18(c) and (d) shows the absorption
and uorescence spectral changes of DAET-FL-labeled ERK protein upon UV and visible irradiation. The new absorption band at 580 nm that appeared after UV irradiation was bleached after visible light irradiation. This band is attributed to absorption by the closed-ring isomer of the DAET moiety. The uorescence band at 520 nm represents emission by the open-ring isomer. Upon irradiation with UV light, the uorescence intensity was signicantly decreased; inten-
Table 5 Structure and properties of DAET derivatives useful in biological applications. Compounds Emission max (nm) Bioapplication Reference
467
Sensing of metal ions
[124]
520
Sensing of Zn ion
[125]
520
Labeling of biomolecules
[132]
520
Imaging of living cell
[134]
127
Fig. 18. (a) Chemical structure of DAE-FL-SE. (b) Photoswitching of uorescence in DAE-FL labeled biomolecule based on the photochromic reaction. (c) Absorption and (d) uorescence spectral change of DAE-FL labeled ERK protein in PBS bufferEtOH (7:3) upon irradiation with UV (365 nm) and visible ( > 550 nm) light. [Original citation]Reproduced by permission of the Royal Society of Chemistry http://dx.doi.org/10.1039/b713663c.
Fig. 19. (a) Structure and photochromism of amphiphilic DAET. (b) Absorption (1) and emission (2) spectral changes of 63o under 365 nm light irradiation (1.0 105 M, ex = 385 nm), (3) uorescence switching of xed KB cells by illumination with alternating UV (405 nm, 2 mW, 10 s/cycle) and visible light (633 nm, 0.7 mW, 20 min/cycle). (c) CLSM image (top) and the overlay image (bottom) of KB cells incubated with 63o for 20 min at 25 C: (1) in original state, (2) single cell irradiated with 405 nm light (2 mW), (3) all cells irradiated with 405 nm light, and (4) uorescence recovered by irradiation with 633 nm light (0.7 mW) ( ex = 405 nm, 0.15 mW). Reprinted with permission from Ref. [132]. Copyright 2008. Journal of The American Chemical Society.
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sity was fully recovered after irradiation with visible light. These results conrm that DAET-FL-SE may be used for the photocontrollable uorescent labeling of biomolecules. Recently, an amphiphilic DAET (compound 63) has been reported as a photoswitchable probe for imaging living cells [134]. Fig. 19(a) shows the amphiphilic DAET molecule composed of hydrophilic and hydrophobic chains at each end of the DAET moiety. This molecule forms stable vesicle nanostructures in aqueous solution. In Fig. 19(b)-1 and (b)-2, a new absorption band at 640 nm appeared after irradiation of colorless compound 63o with UV light (365 nm), and then the absorption band at 640 nm was decreased and uorescence recovered after irradiation with visible light, indicating the photoswitchable nature of this DAET. Such coloration is accompanied by uorescence quenching up to 98% due to the extension of -electron delocalization. After KB cells (human nasopharyngeal epidermal carcinoma cell) were incubated with 20 M of the open-ring isomer of amphiphilic DAET (0.61.0 m in size) in PBS buffer, uorescence in the cytoplasm of the cells was increased to a remarkable extent, as shown in Fig. 19(c)-1. After irradiation of a selected cell with 405 nm light for 3 min, intracellular uorescence was switched off as a result of photochromic conversion to the closed-ring isomer, as shown in Fig. 19(c)-2. Similarly, the uorescence of all the cells was switched off under 405 nm irradiation for 3 min (Fig. 19(c)-3). Interestingly, the uorescence in cells was clearly switched on after exposure to 633 nm light during examination by the confocal laser scanning microscopy (CLSM) lamp for 1 h (Fig. 19(c)-4). Fig. 19(b)-3 shows the reversibility of the on/off uorescence switch in the cell. The high biocompatibility and low toxicity of the amphiphilic DAET was conrmed with an MTT assay and trypan blue staining to measure cell viability. Thus, this amphiphilic DAET represents a novel cell-permeable cellular biomarker with low cytotoxicity.
at an early stage. Various devices and application studies can be designed as photon-mode systems based on photochemical control of the uorescence energy. The photochromic DAET materials have not only shown promise as optical data storage and switching devices, but also as biological applications such as the development of biomaterial sensors, analysis of biological dynamics, and live cell imaging. Based on ndings to date, it would be desirable to conduct additional in-depth research into higher switching stability, improved conductivity, and novel biological applications. Acknowledgment This work was supported by the Korea Science and Engineering Foundation (KOSEF) grant funded by the Korea government (MEST) (No. R11-2007-050-01001-0). References
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4. Conclusions This review summarized the properties of diarylethene (DAET) derivatives, focusing on their photochromic uorescence. These materials represent an organic photoswitching system in which uorescence is switched reversibly by photoirradiation. It has been possible to achieve full color photochromism and luminescence through structural modication including oxidation and polymerization. As an example, DAET and a uorophore such as a PPV monomer were copolymerized to give a copolymer that simultaneously possessed the appropriate photochromic properties and a high uorescent quantum yield. These two properties of the copolymer were selectively controlled by irradiation with specic wavelengths and intensity of light. These properties also promise to advance research into novel multi-functional devices and materials. Quantum chemical (QC) approaches based on ab initio or semiempirical calculations have been performed, either to interpret intriguing experimental observations or to predict photochemical or photophysical properties. In particular, stabilization of HOMO in the BTFOn (n = 1, 2, 3, 4) increases the energy difference between the HOMO and the LUMO, which leads to the blue-shift of absorption and emission bands as the number of oxygen attached to sulfur (n) increases and eventually leads to high uorescence at a closed state. Semi-empirical calculations of absorption spectra for DAET derivatives led to grouping of DAET into two different series: a group consisting only of C, H, F, and S atoms (Class I), and a group comprising N and O in addition to C, H, F, and S (Class II). The absorption maxima ( max ) based on ZINDO-S/AM1, for the closed forms of DAETs belonging to Class I and Class II were compared with experimental results. Despite the increasing necessity of theoretical design parameters to guide DAET synthesis, investigation and assessment of the factors affecting DAET uorescence remains
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Photochromic Fluorescence Switching From Diarylethenes and Its Applications

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Journal of Photochemistry and Photobiology C: Photochemistry Reviews 10 (2009) 111129

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Journal of Photochemistry and Photobiology C: Photochemistry Reviews

Photochromic uorescence switching from diarylethenes and its applications

Scheme 1. The photochromic conversion structures of diarylethene by UV and visible light.

3,4-Ethylenedioxythiophene (EDOT) derivatives

Colorless blue (3), blue (4)

DAET polymer derivatives

Oxidized DAET polymer derivatives

Scheme 2. Interconversion of parallel and anti-parallel conformers in 2.

Fig. 5. The photophysical process in diarylethenes substituted with a uorophore.

Scheme 4. Oxidation of compound 1 [67,83].

Scheme 5. . Molecular structures and photochromism of oxidized derivatives of bis(2-thienyl)ethenes.

Fig. 8. Change in uorescent intensity by the polymerization of 510 [71].

0.093a (in cyclohexane)

530, Light green

0.01a (in cyclohexane)

500, Light blue

620, 523, 561

555, Dark blue

0.38 (in hexane)

0.40 (in hexane)

574, Dark blue

0.36 (in hexane)

Ref. 3-Aminouoranthene (QY = 0.53 in cyclohexane).

Table 4 Chemical structures of DAET in Class I and Class II. Structure

Scheme 7. Photoisomerization of a compound 58 in the pcFRET system.

Scheme 9. Photoisomerization of compound 4.

Sensing of metal ions

Imaging of living cell

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