1 Advanced Control of Photochemical Reactions …
25
the electron transfer from ZnTPP in higher exited states to the imidazole dimer,
which was followed by the rapid bond cleavage in the anion radical of the imidazole
dimer. After the subsequent charge recombination, the neutral radical pair with the
absorption band in the visible region remains. This visible two-photon sensitization
provides the new photosynergetic response of the photochemical reaction taking
place only by the irradiation of the UV light [37]. Also for the protoporphyrin—
CdS/ZnS core/shell nanocrystals (NCs) systems, the electron transfer from higher
excited states of porphyrin pumped by the visible two-photon absorption to CdS NCs
took place and successfully overcame the activation barrier with the wide bandgap
ZnS shell leading to a high reduction potential [38].
It should be noted that, in the case where the initial state of the second photon
absorption is long-lived such as triplet state, the high power of the excitation light
source is unnecessary to induce the stepwise two-photon-gated photochemical reaction. Accordingly, it is expected that the stepwise two-photon excitation can open
many kinds of photosynergetic responses in various kinds of photochemical processes
such as super-resolution microscopy, laser trapping, and so forth.
Acknowledgements We deeply appreciate Professors S. Kobatake, M. Morimoto, M. Irie,
Y. Yokoyama, Y. Kobayashi, K. Matsuda, J. Abe, and K. Uchida for their collaboration. The present
work was supported by JSPS KAKENHI Grant Number 26107002, Grant-in-Aid for Scientific
Research on Innovative Areas “Photosynergetics”.
References
1. Woodward RB, Hoffman R (1969) The conservation of orbital symmetry. Angew Chem Int Ed
8:781–832
2. Irie M (2000) Diarylethenes for memories and switches. Chem Rev 100:1685–1716
3. Irie M, Fukaminato T, Matsuda K, Kobatake S (2014) Photochromism of diarylethene
molecules and crystals: memories, switches, and actuators. Chem Rev 114:12174–12277
4. Yokoyama Y (2000) Fulgides for memories and switches. Chem Rev 100:1717–1739
5. Miyasaka H, Murakami M, Itaya A, Guillaumont D, Nakamura S, Irie M (2001) Multiphoton
gated photochromic reaction in a diarylethene derivative. J Am Chem Soc 123:753–754
6. Murakami M, Miyasaka H, Okada T, Kobatake S, Irie M (2004) Dynamics and mechanisms
of the multiphoton gated photochromic reaction of diarylethene derivatives. J Am Chem Soc
126:14764–14772
7. Ishibashi Y, Okuno K, Ota C, Umesato T, Katayama T, Mutakami M, Kobatake S, Irie M,
Miyasaka H (2010) Multiphoton-gated cycloreversion reactions of photochromic diarylethene
derivatives with low reaction yields upon one-photon visible excitation. Photochem Photobiol
Sci 9:172–180
8. Tani K, Ishibashi Y, Miyasaka H, Kobatake S, Irie M (2008) Dynamics of cyclization, cycloreversion, and multiphoton-gated reaction of a photochromic diarylethene derivative in crystalline
phase. J Phys Chem C 112:11150–11157
9. Piard J, Ishibashi Y, Saito H, Métivier R, Nakatani K, Gavrel G, Yu P, Miyasaka H (2012)
Multiphoton-gated cycloreversion reaction of a photochromic 1,2-bis(hiazolyl)- perfluorocyclopentene diarylethene derivative. J Photochem Photobiol, A 234:57–65
10. Ishibashi Y, Murakami M, Miyasaka H, Kobatake S, Irie M, Yokoyama Y (2007) Laser
multiphoton-gated photochromic reaction of a fulgide derivative. J Phys Chem C 111:2730–
2737
25
the electron transfer from ZnTPP in higher exited states to the imidazole dimer,
which was followed by the rapid bond cleavage in the anion radical of the imidazole
dimer. After the subsequent charge recombination, the neutral radical pair with the
absorption band in the visible region remains. This visible two-photon sensitization
provides the new photosynergetic response of the photochemical reaction taking
place only by the irradiation of the UV light [37]. Also for the protoporphyrin—
CdS/ZnS core/shell nanocrystals (NCs) systems, the electron transfer from higher
excited states of porphyrin pumped by the visible two-photon absorption to CdS NCs
took place and successfully overcame the activation barrier with the wide bandgap
ZnS shell leading to a high reduction potential [38].
It should be noted that, in the case where the initial state of the second photon
absorption is long-lived such as triplet state, the high power of the excitation light
source is unnecessary to induce the stepwise two-photon-gated photochemical reaction. Accordingly, it is expected that the stepwise two-photon excitation can open
many kinds of photosynergetic responses in various kinds of photochemical processes
such as super-resolution microscopy, laser trapping, and so forth.
Acknowledgements We deeply appreciate Professors S. Kobatake, M. Morimoto, M. Irie,
Y. Yokoyama, Y. Kobayashi, K. Matsuda, J. Abe, and K. Uchida for their collaboration. The present
work was supported by JSPS KAKENHI Grant Number 26107002, Grant-in-Aid for Scientific
Research on Innovative Areas “Photosynergetics”.
References
1. Woodward RB, Hoffman R (1969) The conservation of orbital symmetry. Angew Chem Int Ed
8:781–832
2. Irie M (2000) Diarylethenes for memories and switches. Chem Rev 100:1685–1716
3. Irie M, Fukaminato T, Matsuda K, Kobatake S (2014) Photochromism of diarylethene
molecules and crystals: memories, switches, and actuators. Chem Rev 114:12174–12277
4. Yokoyama Y (2000) Fulgides for memories and switches. Chem Rev 100:1717–1739
5. Miyasaka H, Murakami M, Itaya A, Guillaumont D, Nakamura S, Irie M (2001) Multiphoton
gated photochromic reaction in a diarylethene derivative. J Am Chem Soc 123:753–754
6. Murakami M, Miyasaka H, Okada T, Kobatake S, Irie M (2004) Dynamics and mechanisms
of the multiphoton gated photochromic reaction of diarylethene derivatives. J Am Chem Soc
126:14764–14772
7. Ishibashi Y, Okuno K, Ota C, Umesato T, Katayama T, Mutakami M, Kobatake S, Irie M,
Miyasaka H (2010) Multiphoton-gated cycloreversion reactions of photochromic diarylethene
derivatives with low reaction yields upon one-photon visible excitation. Photochem Photobiol
Sci 9:172–180
8. Tani K, Ishibashi Y, Miyasaka H, Kobatake S, Irie M (2008) Dynamics of cyclization, cycloreversion, and multiphoton-gated reaction of a photochromic diarylethene derivative in crystalline
phase. J Phys Chem C 112:11150–11157
9. Piard J, Ishibashi Y, Saito H, Métivier R, Nakatani K, Gavrel G, Yu P, Miyasaka H (2012)
Multiphoton-gated cycloreversion reaction of a photochromic 1,2-bis(hiazolyl)- perfluorocyclopentene diarylethene derivative. J Photochem Photobiol, A 234:57–65
10. Ishibashi Y, Murakami M, Miyasaka H, Kobatake S, Irie M, Yokoyama Y (2007) Laser
multiphoton-gated photochromic reaction of a fulgide derivative. J Phys Chem C 111:2730–
2737