Chapter 21
Giant Amplification of Fluorescence
Quenching in Photochromic
Nanoparticles and Crystals
Tuyoshi Fukaminato, Sanae Ishida, Jia Su, Keitaro Nakatani,
and Rémi Métivier
Abstract Fluorescence photoswitching properties of novel fluorescent
photochromic diarylethene (DAE)-benzothiadiazole (BTD) dyads were studied
in a solution, in the nanoparticle state, and in the single-crystalline state. The
nanoparticles represent a state-of-the-art system, showing bright red emission,
reversible fluorescence photoswitching upon UV-visible irradiation, complete ONOFF contrast, excellent photostability and fatigue resistance. Most interestingly,
upon UV irradiation, the nanoparticles exhibit a complete fluorescence quenching
even at very low conversion (<5%) of the photochromic unit. This “giant amplification of fluorescence quenching” originates from a long-range intermolecular
Förster resonance energy transfer (FRET) within each nanoparticle, leading to the
quenching of ~400 fluorescent molecules for only one converted photochromic
molecule. Furthermore, similar efficient fluorescence photoswitching was observed
even in the single crystal of a DAE-BTD dyad.
Keywords Fluorescence · Diarylethene · Nanoparticles · Single crystals · Energy
transfer · Giant amplification
21.1 Introduction
Molecules which can reversibly change in response to external stimuli are of central
importance to the development of molecular devices and memory materials, but also
pharmacology and imaging technologies [1–5]. Organic photochromic compounds
[6, 7], which reversibly change color under excitation with an appropriate wavelength
of light, are good examples of such molecular systems. They present two stable,
distinct and addressable states. The difference in geometry and electronic structure
T. Fukaminato (B) · S. Ishida
Graduate School of Science and Technology, Department of Applied Chemistry and
Biochemistry, Kumamoto University, Kurokami, Kumamoto 860-8555, Japan
e-mail: tuyoshi@kumamoto-u.ac.jp
J. Su · K. Nakatani · R. Métivier
PPSM, ENS Paris-Saclay, CNRS, Université Paris-Saclay, Gif-sur-Yvette 91190, France
© Springer Nature Singapore Pte Ltd. 2020
H. Miyasaka et al. (eds.), Photosynergetic Responses in Molecules
and Molecular Aggregates, https://doi.org/10.1007/978-981-15-5451-3_21
361
Giant Amplification of Fluorescence
Quenching in Photochromic
Nanoparticles and Crystals
Tuyoshi Fukaminato, Sanae Ishida, Jia Su, Keitaro Nakatani,
and Rémi Métivier
Abstract Fluorescence photoswitching properties of novel fluorescent
photochromic diarylethene (DAE)-benzothiadiazole (BTD) dyads were studied
in a solution, in the nanoparticle state, and in the single-crystalline state. The
nanoparticles represent a state-of-the-art system, showing bright red emission,
reversible fluorescence photoswitching upon UV-visible irradiation, complete ONOFF contrast, excellent photostability and fatigue resistance. Most interestingly,
upon UV irradiation, the nanoparticles exhibit a complete fluorescence quenching
even at very low conversion (<5%) of the photochromic unit. This “giant amplification of fluorescence quenching” originates from a long-range intermolecular
Förster resonance energy transfer (FRET) within each nanoparticle, leading to the
quenching of ~400 fluorescent molecules for only one converted photochromic
molecule. Furthermore, similar efficient fluorescence photoswitching was observed
even in the single crystal of a DAE-BTD dyad.
Keywords Fluorescence · Diarylethene · Nanoparticles · Single crystals · Energy
transfer · Giant amplification
21.1 Introduction
Molecules which can reversibly change in response to external stimuli are of central
importance to the development of molecular devices and memory materials, but also
pharmacology and imaging technologies [1–5]. Organic photochromic compounds
[6, 7], which reversibly change color under excitation with an appropriate wavelength
of light, are good examples of such molecular systems. They present two stable,
distinct and addressable states. The difference in geometry and electronic structure
T. Fukaminato (B) · S. Ishida
Graduate School of Science and Technology, Department of Applied Chemistry and
Biochemistry, Kumamoto University, Kurokami, Kumamoto 860-8555, Japan
e-mail: tuyoshi@kumamoto-u.ac.jp
J. Su · K. Nakatani · R. Métivier
PPSM, ENS Paris-Saclay, CNRS, Université Paris-Saclay, Gif-sur-Yvette 91190, France
© Springer Nature Singapore Pte Ltd. 2020
H. Miyasaka et al. (eds.), Photosynergetic Responses in Molecules
and Molecular Aggregates, https://doi.org/10.1007/978-981-15-5451-3_21
361