15 Solid-State Fluorescence Switching Using Photochromic …
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inverse-type diarylethene 1a and the derivatives exhibit different fluorescence colors
depending on the intermolecular interaction in different states. In addition, 18a21a have crystallization-induced emission (CIE) characteristics to exhibit strong
fluorescence in the crystalline phase compared in n-hexane and in the amorphous
phase (Fig. 15.17b). The amorphous solid of 18a which has the most remarkable
CIE characteristics among 18a-21a was crystallized after mechanical scratching
followed by heating at 90 °C because the small crystal nuclei were fabricated by
scratching and the growth of the crystal nuclei was performed by heating. As shown
in Fig. 15.17c, reversible fluorescence recording based on CIE characteristics and
mechanical scratching and heating induced crystallization was successfully demonstrated. By partly scratching and heating at 90 °C for 3 min for the amorphous solid
that was prepared by heating the crystals at 150 °C, green fluorescent letters of “D”
or “E” were clearly written. The letter was completely erased by heating at 150 °C for
30 s. As introduced up to this point, inverse-type diarylethenes having phenyl groups
show unique behavior in the solid states, such as multicolor fluorescence depending
on intermolecular interactions and responsiveness for external stimuli such as heat
and scratching, which may be useful for potential applications such as in sensors and
security materials.
15.5 Summary
In this chapter, we have introduced the solid-state fluorescence switching using
diarylethene. The fluorescence switching can be achieved by combining a
diarylethene with a fluorophore or using a fluorescent diarylethene in solution. On
the other hand, in the solid states, it is difficult to obtain similar properties as in
solution due to problems such as concentration quenching and environmental effect
of the matrix. However, various types of solid-state fluorescence-switchable systems
using the diarylethenes based on rational molecular design and smart experimental
approach have been proposed and successfully demonstrated for practical applications, such as optical memory, display devices, and sensor materials. A series of the
researches will advance the realization of the applications based on the fluorescence
switching of the diarylethene.
References
1. Irie, M., Fukaminato, T., Matsuda, K., Kobatake, S.: Photochromism of diarylethene molecules
and crystals: memories, switches, and actuators. Chem. Rev. 114, 12174–12277 (2014)
2. Fukaminato, T., Kobatake, S., Kawai, T., Irie, M.: Three-dimensional erasable optical memory
using a photochromic diarylethene single crystal as the recording medium. Proc. Japan Acad.,
Ser B 77, 30–35 (2001)
3. Fukaminato, T., Kawai, T., Kobatake, S., Irie, M.: Fluorescence of photochromic 1,2-bis(3methyl-2-thienyl)ethene. J. Phys. Chem. B 107, 8372–8377 (2003)
319
inverse-type diarylethene 1a and the derivatives exhibit different fluorescence colors
depending on the intermolecular interaction in different states. In addition, 18a21a have crystallization-induced emission (CIE) characteristics to exhibit strong
fluorescence in the crystalline phase compared in n-hexane and in the amorphous
phase (Fig. 15.17b). The amorphous solid of 18a which has the most remarkable
CIE characteristics among 18a-21a was crystallized after mechanical scratching
followed by heating at 90 °C because the small crystal nuclei were fabricated by
scratching and the growth of the crystal nuclei was performed by heating. As shown
in Fig. 15.17c, reversible fluorescence recording based on CIE characteristics and
mechanical scratching and heating induced crystallization was successfully demonstrated. By partly scratching and heating at 90 °C for 3 min for the amorphous solid
that was prepared by heating the crystals at 150 °C, green fluorescent letters of “D”
or “E” were clearly written. The letter was completely erased by heating at 150 °C for
30 s. As introduced up to this point, inverse-type diarylethenes having phenyl groups
show unique behavior in the solid states, such as multicolor fluorescence depending
on intermolecular interactions and responsiveness for external stimuli such as heat
and scratching, which may be useful for potential applications such as in sensors and
security materials.
15.5 Summary
In this chapter, we have introduced the solid-state fluorescence switching using
diarylethene. The fluorescence switching can be achieved by combining a
diarylethene with a fluorophore or using a fluorescent diarylethene in solution. On
the other hand, in the solid states, it is difficult to obtain similar properties as in
solution due to problems such as concentration quenching and environmental effect
of the matrix. However, various types of solid-state fluorescence-switchable systems
using the diarylethenes based on rational molecular design and smart experimental
approach have been proposed and successfully demonstrated for practical applications, such as optical memory, display devices, and sensor materials. A series of the
researches will advance the realization of the applications based on the fluorescence
switching of the diarylethene.
References
1. Irie, M., Fukaminato, T., Matsuda, K., Kobatake, S.: Photochromism of diarylethene molecules
and crystals: memories, switches, and actuators. Chem. Rev. 114, 12174–12277 (2014)
2. Fukaminato, T., Kobatake, S., Kawai, T., Irie, M.: Three-dimensional erasable optical memory
using a photochromic diarylethene single crystal as the recording medium. Proc. Japan Acad.,
Ser B 77, 30–35 (2001)
3. Fukaminato, T., Kawai, T., Kobatake, S., Irie, M.: Fluorescence of photochromic 1,2-bis(3methyl-2-thienyl)ethene. J. Phys. Chem. B 107, 8372–8377 (2003)