Chapter 1
Advanced Control of Photochemical
Reactions Leading to Synergetic
Responses in Molecules and Mesoscopic
Materials
Hiroshi Miyasaka, Hikaru Sotome, and Syoji Ito
Abstract In the present chapter, we first introduce the mechanism of the
multiphoton-gated photochromic reactions in diarylethene and fulgide derivatives
by pulsed laser excitation, where the multiple photons lead to the specific photoresponse beyond the Kasha’s rule. In the second part, we discuss the one-color control
of the activation, deactivation, and fluorescence excitation in the single-molecule
detection. One-color of light takes various roles resulting in the effective singlemolecule tracking via the photon-material synergetic response. In the third section,
photochromic reaction is applied to the controlled translational motion of nano- to
micron-sized materials under the laser trapping. Integrated photoresponses of materials, such as absorption, photochemical reaction, and the photon pressure, lead to
the mesoscopic motion synchronized with the photochemical reaction.
Keywords Multiphoton excitation · Multiple excitation · Diarylethene · Fulgide ·
Ultrafast laser pulse · Single-molecule tracking · Photon pressure
1.1 Introduction
The property and reactivity of molecules are dependent on the electronic states and,
accordingly, we can expect various photoresponses of molecules by changing the
irradiation wavelength and the mode of the excitation. However, specific reaction
depending on the high electronic state is very rare for polyatomic molecules due
to the rapid internal conversion in the highly excited state (Kasha’s rule). In the
present chapter, we first introduce the multiphoton-gated cycloreversion reaction of
diarylethene and fulgide derivatives as one of photosynergetic responses beyond the
Kasha’s rule. In these systems, marked enhancement of the cycloreversion reaction
takes place in specific electronic states attained only by the two-photon absorption.
We discuss the mechanism of the multiphoton-gated reaction on the basis of the
H. Miyasaka (B) · H. Sotome · S. Ito
Division of Frontier Materials Science, Graduate School of Engineering Science,
Osaka University, Toyonaka, Osaka 560-8531, Japan
e-mail: miyasaka@chem.es.oasaka-u.ac.jp
© 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_1
3
Advanced Control of Photochemical
Reactions Leading to Synergetic
Responses in Molecules and Mesoscopic
Materials
Hiroshi Miyasaka, Hikaru Sotome, and Syoji Ito
Abstract In the present chapter, we first introduce the mechanism of the
multiphoton-gated photochromic reactions in diarylethene and fulgide derivatives
by pulsed laser excitation, where the multiple photons lead to the specific photoresponse beyond the Kasha’s rule. In the second part, we discuss the one-color control
of the activation, deactivation, and fluorescence excitation in the single-molecule
detection. One-color of light takes various roles resulting in the effective singlemolecule tracking via the photon-material synergetic response. In the third section,
photochromic reaction is applied to the controlled translational motion of nano- to
micron-sized materials under the laser trapping. Integrated photoresponses of materials, such as absorption, photochemical reaction, and the photon pressure, lead to
the mesoscopic motion synchronized with the photochemical reaction.
Keywords Multiphoton excitation · Multiple excitation · Diarylethene · Fulgide ·
Ultrafast laser pulse · Single-molecule tracking · Photon pressure
1.1 Introduction
The property and reactivity of molecules are dependent on the electronic states and,
accordingly, we can expect various photoresponses of molecules by changing the
irradiation wavelength and the mode of the excitation. However, specific reaction
depending on the high electronic state is very rare for polyatomic molecules due
to the rapid internal conversion in the highly excited state (Kasha’s rule). In the
present chapter, we first introduce the multiphoton-gated cycloreversion reaction of
diarylethene and fulgide derivatives as one of photosynergetic responses beyond the
Kasha’s rule. In these systems, marked enhancement of the cycloreversion reaction
takes place in specific electronic states attained only by the two-photon absorption.
We discuss the mechanism of the multiphoton-gated reaction on the basis of the
H. Miyasaka (B) · H. Sotome · S. Ito
Division of Frontier Materials Science, Graduate School of Engineering Science,
Osaka University, Toyonaka, Osaka 560-8531, Japan
e-mail: miyasaka@chem.es.oasaka-u.ac.jp
© 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_1
3