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The Use of Diarylethene Derivatives for Photo-Switching

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The Use of Diarylethene Derivatives for Photo-Switching Contribution The use of Diarylethene Derivatives for Photo-switching Kenji Matsuda Masahiro Irie Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University 1. Introduction The color change is attributable to the different electrical structures between the open-ring and closed-ring The process of reversible coloration changes induced isomers. In the open-ring isomers, free rotation exists at at least in one-direction by photoirradiation is referred to the ethene and aryl groups, so the isomer is non-planar as photochromism.1) The two isomers of photochromic com- and the π-electrons are localized in the two aryl groups. pounds differ in their geometrical and electrical structures. Furthermore, due to rotational energy barriers, two rota- These geometrical and electrical differences lead to tional isomers exist, namely, photo-reactive (anti-parallel) changes in the physical properties of the molecules, such and photo-inactive (parallel) (Figure 2).3) On the other hand, as their absorption and fluorescence spectra, refractive the closed ring isomer possesses high planarity, with index and electrical conductivity. Since the transformation asymmetrically arranged carbon atoms at the reaction site. between the isomers is induced by photoirradiation, It has a bond alternation polyene structure and a π-conju- optical-switching of the physical properties can be realized gated system spread throughout the molecule. Reflecting by using the photochromic units. on the differences between these geometric and electrical Diarylethene, which contains five-membered structures, their physical properties vary in many ways.4) heterocyclic rings, is well known as a photochromic com- In this review, some of the physical properties that were pound that is thermo-irreversible, has high-sensitivity and photo-switched by using photochromic diarylethene units, has fatigue resistance properties.2) Photochromic reactions i.e. the functions of fluorescent switching, dielectric in diarylethene take place between two isomers, (hexatriene switching and magnetic switching, are discussed in terms and cyclohexadiene) following the Woodward-Hoffmann of molecular design and their correlation with the structural rule (Figure 1). The open-ring isomer, hexatriene 1a, is properties. generally colorless, but the closed-ring, cyclohexadiene isomer 1b, develops yellow, red and blue coloration, depending on the substituents. F2 F2 F2 F2 CH H3C3 F2 F2 CH3 SS H3C CH3 R H C S S 3 R R H3C RCH 2 5 UV 2 5 3 R R R R antiparallel R1 R1 parallel 3 4 R6 Vis. 3 R6 R X R Y R X R4 Y Vis. UV 1a 1b F2 F2 F2 H3CCH3 Figure 1. Photochromism in diarylethene. CH3 R S S R H3C Figure 2. Conformation of diarylethene. 2. Fluorescent Switches F2 2.1. Fluorescent Switching F2 F2 CH3 CH3 For the application of photochromic compounds to S S optical memory media, one essential function that is H3C CHO required is a non-destructive readout capability. The con- 3a fluorecent ventional “transmittance readout method” could damage the recorded data due to the photochromic reactions that it F2 might undergo, depending on the type of light that is used F2 F2 UV CH for the readout. On the other hand, “fluorescent readout 3 CH3 method” is highly sensitive that is able to achieve detec- Vis. S S tion with minimal damage to the data.5) H3C CHO Various fluorescent switching molecules have been 3b non-fluorecent synthesized. Figure 3 shows a fluorescent switching diarylethene that Lehn et al. developed.6) In methanol, the Figure 4. open-ring isomer 2a conversts to the closed-ring isomer 2b when irradiated with light below 400 nm upto conver- sion rate of 92%. The closed-ring isomer 2b quantitatively Triphenylimidazole is a well-known compound that returned bade to the open-ring isomer 2a upon irradiation possesses a high fluorescent quantum yield (48%). with light of above 600 nm. The open-ring isomer emits Diarylethene 4 with triphenylimidazole as a substituent was fluorescence at 589 nm upon excitation with 459 nm light, synthesized. (Figure 5).8) The open-ring isomer 4a emitted which is the absorption maximum of pyridyl- fluorescence at 390 and 410 nm upon excitation with 313 diphenothiophen-thiophenes, while the closed-ring isomer nm light in hexane solution with a fluorescence quantum does not emit any fluorescence. In short, the fluorescence yield of 7.7%, while 4b did not emit any fluorescence. is ON in the open-ring isomer but is OFF in the closed-ring isomer. Furthermore, both cyclization and cycloreversion reactions are hardly induced by excitation with 459 nm light. F2 Therefore, it can be used as a non-destructive readout F2 F2 method. CH3 CH3 H C 3 S H3C S N 4a HN F2 fluorescent F2 F2 Hex CH H3C N S S S S N 3 S S Hex F2 S S F F 2a fluorescent 2 2 UV CH3 UV Vis. CH3 H C S S Vis. 3 H3C F2 N F2 F2 4b HN non-fluorescent CH H3C N S S Hex S S N 3 S Hex S S S 2b non-fluorescent Figure 5. Diarylethene 4. Osuka et al. successfully synthesized diarylethene- Figure 3. Diarylethane 2. substituted tetraphenylporphyrin 5 and reported its fluores- cent behavior (Figure 6).9) The open-ring form 5a gener- ated fluorescence at 650 nm and 717 nm upon Diarylethene with 4-formylphenylthiophene 3 (Figure excitation with 420 nm light. However, the intensity of the 4) was also reported to show fluorescent switching behav- fluorescence became weaker for the closed ring form, 5b. ior.7) The open-ring isomer 3a has a strong fluorescent It was suggested that the excited energy of the diarylethene emission at 420 nm when excited with 301 nm light, but closed-ring form was transferred from the excited state of the closed-ring isomer does not exhibit any fluorescence. porphyrin. The conversion rate of the photostationary state upon irradiation with 330 nm light was determined as 75%. The cyclization and cycloreversion quantum yields were determined to be 4.3 × 10-2 and 1.8 × 10-3, respectively. F2 F2 F2 CH3 S H3C S 5a strongly fluorescent N N N H H N H N N H N N UV Vis. F2 F2 F2 CH3 S H3C S 5b N weakly fluorescent N N H H N H N N H N N Figure 6. Diarylehtene 5. F2 F2 F2 F2 F2 F2 CH3 H3C CH3 CH3 H3C CH3 S H3C S S H3C S 6a fluorescent UV Vis. F2 F2 F2 F2 F2 F2 CH3 H3C CH3 CH3 H3C CH3 S H3C S S H3C S 6b non-fluorescent Figure 7. Diarylethene 6. Figure 7 shows fluorescent bis(phenylethynyl)anthra- 2.2. Photoluminescence of Metal Complexes cene 6, which has two diarylethene groups.10) The fluores- cence quantum yield of the anthracene 6a was 0.83, while Branda et al. reported the phosphorescence switching ring-closure of the diarylethene ring decreased the quan- of a transition metal complex (Figure 8).11) 7a is a tum yield significantly to 0.001. Furthermore, the open-ring ruthenium complex, which is based on rutheniumporphyrins isomer 6a underwent laser emission upon excitation with a axially coordinated to pyridyl ligands. The open-ring 337.1 nm pulsed laser. The laser emission intensity could isomer 7a convered to the closed-ring isomer 7b when be photo-switched by the photoreaction of the diarylethene irradiated with 365 nm light upto a conversion rate of 95%. units. F2 F2 F2 CH3 H3C CH3 H C CH3 3 S H3C S N N N N 7a N NRu NRu N N N OC CO CH3 H3C H3C CH3 phosphorescent UV Vis. F2 F2 F2 CH3 H3C CH3 H C CH3 3 S H3C S N N N N N 7b NRu NRu N N N OC CO CH3 H3C non-phosphorescent H3C CH3 Figure 8. Diarylethene 7. F2 F2 F F2 F2 2 F2 CH CH3 3 non-fluorescent S H3C S S H3C S N HO 8a W(CO)5 9a emission maximum : 450nm UV Vis. UV Vis. F2 F2 F F2 F2 2 F2 CH CH3 3 fluorescent S H3C S S H3C S N HO 8b W(CO)5 9b emission maximum : 650nm Figure 9. Diarylethene 8. Figure 10. Diarylethene 9. The closed-ring isomer reverted to the open-ring isomer Also, irradiation with 240 nm light has little effect on the upon irradiation with 470-685 nm light. The open-ring photochromic reactions. This result demonstrates that the isomer 7a phosphoresces at 730 nm when excited with system is non-destructive under these conditions and could 400-480 nm light. In contrast, the closed-ring isomer 7b be applied to a non-destructive readout method. did not phosphoresce. Excitation with 400-480 nm light did Diarylethene 9 is also reported as a compound that not affect the photochromic reactions in either direction. photoluminesces in the closed ring form (Figure 10).13) The Consequently, the compound can provide a non-destruc- open-ring isomer 9a fluoresces with the emission maximum tive readout method. at 450 nm (fluorescence quantum yield of 1.1), but in the The tungsten complex 8 showed a different response closed-ring isomer 9b, the emission maximum shifted to to those we have just described. The closed-ring form fluo- 650 nm and the yield decreased significantly. resces more strongly than the open ring form (Figure 9).12) The fluorescence quantum yield was 0.15 for the closed- ring isomer 8b, and was 0.03 for the open-ring isomer 8a. 2.3. Photochromism at a Single-Molecule Level Photochromic molecules can give useful performances even at the single-molecule level. If a single molecule worked as one bit of memory, then ultimately a high- density optical memory could be realized.
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