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Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2013; 17: 821–830
Synthesis and photophysical properties of a
porphyrin-perinaphthothioindigo dye
Kazuya Ogawa*a†◊, Joanne Dya, Rena Maedaa, Yasunori Nagatsukaa,
Kenji Kamada*b andYoshiaki Kobuke*a††
a Graduate School of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma,
Nara 630-0101, Japan
b Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science
and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, Japan
Dedicated to Professor Evgeny Luk’yanets on the occasion of his 75th birthday
Received 15 February 2013
Accepted 3 April 2013
ABSTRACT: A new porphyrin-perinaphthothioindigo composite, where porphyrin and perinaph-
thothioindigo dye are connected though a triple bond, was synthesized. In UV-vis absorption spectra of
the composite, absorption originating from the trans-isomer appeared at 655 nm. Upon photoirradiation
at >700 nm, the intensity of this absorption decreased with increase of absorption of the cis-isomer
around at 530 nm. The HOMO–LUMO absorption of the cis-isomer is blue-shifted by 125 nm compared
to that of trans-isomer due to the lack of p-conjugation. The 2PA cross-section values obtained for both
isomers were 2,000 and 700 GM, respectively. The value of 2,000 GM is of the largest class among the
values reported for photochromic compounds. The enhancement factors by the connection of porphyrin to
perinaphthothioindigo were found to be 3.5–3.9 by measuring cross-section values of bis(TMS-ethynyl)
perinaphthothioindigo as the reference compound. Two-photon isomerization of the trans-isomer to the
cis-isomer was successfully conducted using femtosecond pulses.
KEYWORDS: porphyrin, perinaphthothioindigo, two-photon absorption, 3D optical memory,
photochromism.
on the laser intensity allows spatial selectivity using a
INTRODUCTION
focused laser beam. This characteristic feature permits a
Two-photon absorption (2PA) is a third-order nonlinear
wide variety of optical applications such as photodynamic
phenomenon,whereinexcitationoccursbythesimultaneous
therapy (PDT) [1–3] and three dimensional (3D) optical
absorption of two photons. The quadratic dependence
data storage [4–9]. Usually, the study of molecular optical
memory employs a reversible photochromic transformation
between two chemical species on absorbing light at a
◊ SPP full member in good standing
specific wavelength, where the two species have different
absorption and/or emission properties. This property
change can be used to record information as the photon-
mode optical memory. Some two-photon photochromic
compounds have been reported such as diarylethene
derivatives that exhibited two-photon photochromism
bearing a maximum 2PA cross-section value of ~44 GM
(1 GM = 10-50 cm4.s.molecule-1.photon-1) at 770 nm [10] and
an indolylfulgide yielding a maximum value of 1,030 GM
at a wavelength of 775 nm [11]. Unfortunately, the currently
*Correspondence to: Kazuya Ogawa, tel: +81 55-220-8511,
fax: +81 55-220-8511, email: kogawa@yamanashi.ac.jp; Kenji
Kamada, tel: +81 72-751-9523, fax: +81 72-751-9637, email:
k.kamada@aist.go.jp; Yoshiaki Kobuke, tel: +81 774-38-4581,
fax: +81 774-38-4577, email: kobuke@iae.kyoto-u.ac.jp
†Current address: Interdisciplinary Graduate School of Medical
and Engineering, Division of Medicine and Engineering
Science, Life Environment Medical Engineering, University of
Yamanashi, 4-3-11 Takeda, Kofu, Yamanashi 400-8511, Japan
††Current address: Institute ofAdvanced Energy, Kyoto University,
Gokasho, Uji, Kyoto 611-0011, Japan
Copyright © 2013 World Scientific Publishing Company